Bituminous composition comprising biochar and a plasticising agent

Abstract

The present invention relates to a bituminous composition comprising: a) at least one bitumen base, b) biochar, and c) at least one plasticising agent.

Description

[0001] BITUMINOUS COMPOSITION COMPRISING BIOCHAR AND A PLASTICIZING AGENT

[0002] The present invention relates to a bituminous composition comprising bitumen, biochar and at least one plasticizing agent. The invention also relates to a method for preparing or the use of a bituminous composition according to the invention, in particular for road and / or industrial applications.

[0003] Bitumen is the main hydrocarbon component used in road construction and civil engineering. It is used, for example, in the production of road surfaces and waterproofing membranes. Bitumen is generally obtained from residues from the atmospheric and / or vacuum distillation of crude oil.

[0004] Oil resources are, however, limited. Indeed, "proven reserves" of oil reached more than 200 billion tonnes of oil equivalent (TOE) worldwide in 2018, according to experts at 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.

[0005] Furthermore, oil exploitation is responsible for the release of significant quantities of greenhouse gases into the atmosphere, which have a significant impact on global warming. It is therefore necessary to limit our consumption of oil, particularly bitumen, in order to minimize the overall rise in Earth's temperatures.

[0006] In order to maintain and / or improve the characteristics, in particular the mechanical properties, of a conventional bitumen, it is also known to use crosslinked 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 road surfacing applications. The carbon footprint associated with these bitumen / polymer compositions is, however, much higher than that of pure bitumen. 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 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. There is therefore still a need for bituminous compositions, particularly bitumen / polymer compositions, with a significantly reduced carbon footprint.

[0007] WO 2022 / 032152 describes the preparation of bituminous compositions incorporating biochar. However, this document does not describe compositions additionally incorporating a plasticizing agent. Furthermore, it does not deal with bitumen / polymer compositions, possibly crosslinked.

[0008] There therefore remains a need for bituminous compositions whose content of material(s) of fossil origin, in particular derived from petroleum, is reduced compared to the compositions of the prior art.

[0009] In particular, there remains a need for bituminous compositions having mechanical properties, in particular elastic properties, which are improved compared to the polymer-free compositions of the prior art, and whose content of material(s) of fossil origin, in particular derived from petroleum, is reduced compared to the compositions of the prior art.

[0010] Even more particularly, there remains a need for bitumen / polymer compositions (possibly crosslinked) whose content of material(s) of fossil origin, in particular derived from petroleum, is reduced compared to the compositions of the prior art.

[0011] There also remains a need to provide bituminous compositions with a reduced carbon footprint, compared to prior art compositions.

[0012] In particular, there remains a need for bituminous compositions having mechanical properties, in particular elastic properties, which are improved compared to the polymer-free compositions of the prior art, and whose carbon footprint is reduced compared to the compositions of the prior art.

[0013] Even more particularly, there remains a need for bitumen / polymer compositions (possibly crosslinked) whose carbon footprint is reduced, compared to the compositions of the prior art.

[0014] During its previous work, the Applicant discovered that it was possible to reduce the content of material(s) of fossil origin by integrating one or more biochar(s) into a bituminous composition, in particular into a bitumen / polymer composition. In particular, the Applicant discovered that it was possible to reduce the carbon footprint of the bituminous compositions of the prior art, in particular bitumen / polymer compositions, by integrating biochar. The compositions obtained have entirely satisfactory properties both for their application as a road binder and for the preparation of membranes. The compositions in fact comply with all the specifications imposed.

[0015] The Applicant has, however, noted that the incorporation of biochar results in a degradation of certain properties of the bituminous composition. In particular, the Applicant has noticed that the incorporation of biochar results in a slight degradation of the cold resistance of the composition, as well as a drop in the mechanical properties of the composition, in particular its elongation at break, compared to a bituminous composition free of biochar.

[0016] There therefore remains a need to provide bituminous compositions with a reduced carbon footprint, thanks to the incorporation of biochar, and with improved properties, in particular in terms of cold resistance and / or elastic properties. In particular, there remains a need to provide biochar-based bituminous compositions, and with equivalent, or even improved, properties compared to biochar-free bituminous compositions, in particular in terms of cold resistance and elastic properties.

[0017] In continuation of its work, the Applicant discovered that it was possible to compensate for the deterioration of the mechanical properties of the bituminous composition caused by the incorporation of biochar by the addition of one or more plasticizing agents. In particular, the Applicant discovered that the incorporation, in a bituminous composition comprising biochar, of one or more plasticizing agents made it possible to improve certain of the mechanical properties of the composition, in particular the cold resistance and / or the elongation at break of the composition.

[0018] Summary of the invention

[0019] The invention firstly relates to a bituminous composition comprising:

[0020] - at least one bitumen base,

[0021] - biochar, and

[0022] - at least one plasticizing agent.

[0023] Preferably, the plasticizing agent is chosen from: a) tall oil derivatives, b) plastic pyrolysis oils, c) triglycerides d) mixtures of a) and / or b) and / or c).

[0024] Advantageously, the biochar is derived from the thermochemical conversion of biomass selected from forest products; crop residues; animal waste; municipal waste and any mixture thereof. More advantageously, the biochar is derived from the thermochemical conversion of biomass selected from hardwoods, in particular ash wood; grain husks; nut shells, in particular cashew nuts; food waste; coffee grounds and any mixture thereof.

[0025] Preferably, the composition of the invention has a biochar content ranging from 0.1% to 50% by mass, preferably from 0.5% to 30% by mass, preferably from 1% to 15% by mass, relative to the total mass of the bituminous composition.

[0026] 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.

[0027] 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.

[0028] The invention also relates to a process for preparing a bituminous composition according to the invention, this process comprising:

[0029] 1) bringing the following components into contact:

[0030] - at least one bitumen base,

[0031] - biochar, and

[0032] - at least one plasticizing agent

[0033] 2) mixing the components.

[0034] Preferably, the mixing of the components is carried out under heating and stirring, preferably at a temperature ranging from 90°C to 230°C, more preferably from 120°C to 200°C, even more preferably from 150°C to 180°C.

[0035] The invention also relates to the use of a bituminous composition according to the invention, 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.

[0036] 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.

[0037] The invention also relates to an asphalt comprising a bituminous composition according to the invention, mixed with mineral and / or synthetic fillers.

[0038] The invention also relates to a waterproofing coating, preferably a membrane or an impregnation layer, comprising a bituminous composition according to the invention. The invention also relates to the use in a bituminous composition, in particular in an optionally crosslinked bitumen / polymer composition, of the combination of at least one biochar and at least one plasticizing agent, to reduce the content of compound(s) of fossil origin in said composition.

[0039] The invention finally relates to the use in a bituminous composition, in particular in an optionally crosslinked bitumen / polymer composition, of the combination of at least one biochar and at least one plasticizing agent, to reduce the carbon footprint of said composition.

[0040] Detailed description of the invention

[0041] 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).

[0042] Likewise, and unless explicitly stated otherwise, the standards mentioned in the remainder of the description correspond to the standard in force on the date of 1 er December 2022.

[0043] The invention firstly relates to a bituminous composition comprising:

[0044] - at least one bitumen base,

[0045] - biochar, and

[0046] - at least one plasticizing agent.

[0047] Bitumen base

[0048] The bitumen(s) used to prepare a bitumen / polymer composition according to the invention are called “bitumen base”.

[0049] 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 oil 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.

[0050] Different bitumens obtained by 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.

[0051] Generally, blowing is carried out at high temperatures, in the order of 200 to 300°C, for relatively long periods of time, 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 the quality of the starting bitumen.

[0052] Among the bitumens that can be used according to the invention, recycling bitumens can also be mentioned.

[0053] Bitumens can be hard grade bitumens (such as grades 10 / 20 and 20 / 30) or soft grade bitumens (such as grade 160 / 220) as defined by EN 12591.

[0054] 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.

[0055] 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 by means of 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). The 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.Preferably, the bituminous composition according to the invention comprises at least 40% by mass of bitumen, relative to the total mass of the bituminous 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.

[0056] Advantageously, the bituminous composition according to the invention comprises from 40% to 99.9% by mass of bitumen, relative to the total bituminous composition, preferably from 50% to 99% by mass, more preferably from 60% to 95% by mass, even more preferably from 70% to 95% by mass, advantageously from 75% to 95% by mass, more advantageously from 80% to 95% by mass.

[0057] Biochar

[0058] The bituminous composition according to the invention also comprises biochar.

[0059] According to the International Biochar Initiative (IBI), biochar is defined as a solid material obtained by thermochemical conversion, particularly by heating and / or pyrolysis, of biomass in an oxygen-limited environment, or even in the total absence of oxygen. In particular, the thermochemical conversion of biomass results in a complex mixture consisting mainly of hydrocarbon compounds of varying chain lengths. The mixture is then separated into different fractions based on their evaporation temperature. This produces a gaseous fraction, a (bio)fuel fraction, an oily fraction, and also a residue. This distillation residue then constitutes biochar.

[0060] Biochar differs from charcoal in its use (as a material of interest rather than as fuel) and therefore in its environmental impact. Biochar thus constitutes a carbon sink, unlike charcoal, the combustion of which releases carbon dioxide into the atmosphere. In addition, biochar generally comes in powder form, while charcoal comes in lump form.

[0061] The chemical and physical properties of biochar depend on several parameters including the nature of the starting biomass (“feedstock” in English) but also the parameters of the thermochemical conversion process, in particular the pyrolysis conditions.

[0062] The nature of the starting biomass is not particularly limited. Thus, the biochar present in the composition according to the invention can come from the thermochemical conversion of any type of biomass. Typically, the biochar present in the composition according to the invention comes from the thermochemical conversion of biomass chosen from forest products; agricultural crop residues; animal waste; municipal waste and any of their mixtures.

[0063] Forest products include hardwoods (also called hardwoods) such as maple, oak, ash, cherry, walnut, apple, and pear; and softwoods such as conifers such as pine, spruce, and fir. Forest products may also include leaves, thorns, and fruit (acorns, pine cones, etc.).

[0064] Preferably, forest products are chosen from hardwoods, more preferably ash wood.

[0065] Crop residues include straw, such as corn straw, wheat straw or rice straw; bagasse (fibrous residue) obtained by grinding sugar cane; cereal husks; peanut shells; nut shells, such as almonds, Brazil nuts, cashew nuts, hazelnuts, pecans or walnuts.

[0066] For the purposes of the invention, the term "cereal husks" or "berry" (or even "basel") means a co-product derived from the processing of cereals and consisting of the glumes and glumes which enclose the grain. In other words, cereal husks constitute the envelope in which the grain of the cereals is contained.

[0067] Examples include corn husks, wheat husks, barley husks, sorghum husks, wheat husks, spelt husks and husks of any other cereal.

[0068] Preferably, the crop residues are chosen from cereal husks, nut shells, especially cashew nuts, and any of their mixtures.

[0069] Animal waste includes slurry, manure and bedding from livestock, particularly poultry, pigs and cattle.

[0070] Municipal waste includes food waste, including organic waste such as peelings and coffee grounds, and municipal biosolids.

[0071] For the purposes of the invention, the term "municipal biosolids" or sewage sludge means the material resulting from the treatment of municipal wastewater and which is of sufficient quality to be recycled. It consists mainly of organic matter.

[0072] Preferably, the municipal waste is selected from food waste, coffee grounds and any of their mixtures. According to a preferred embodiment, the biomass is selected from hardwoods, in particular ash wood; cereal husks; nut shells, in particular cashew nuts; food waste; coffee grounds and any of their mixtures.

[0073] According to a further preferred embodiment, the biomass is chosen from ash wood, cereal husks, cashew nut shells, coffee grounds and any of their mixtures.

[0074] The process for converting biomass into biochar is not particularly limited. In particular, any thermochemical conversion process known to those skilled in the art can be implemented for the preparation of biochar usable in the compositions. Suitable conversion processes are for example described in Chapter 2 “Biochar for Maintaining Soil Health” of the book B. Giri, A. Varma (eds.), Soil Health / , Soil Biology 59. A. Tomczyk et al., “Biochar physichemical properties: pyrolysis temperature and feedstock kind effects”, Rev Environ Sci Biotechnol, February 5, 2020 also studies the impact of the choice of biomass and thermochemical conversion conditions on the nature of the final biochar.

[0075] The conversion of biomass into biochar is typically carried out at a temperature greater than or equal to 350°C, preferably ranging from 350°C to 900°C.

[0076] Preferably, the biochar has a high carbon content C, typically greater than 20% by mass, relative to the total mass of biochar, more preferably greater than or equal to 50%.

[0077] Advantageously, the biochar has a carbon content (also called total carbon content), determined by elemental analysis, ranging from 20% to 80% by mass, relative to the total mass of biochar, more preferably from 50% to 75% by mass.

[0078] For the purposes of the invention, the term "biogenic carbon" means the proportion of carbon present in the biochar coming directly from the biomass, in particular the proportion of carbon fixed by the initial biomass following a photosynthesis mechanism using CO2 from the air. Biogenic carbon is thus distinguished from fossil carbon, in particular by a difference in the ratio between the quantity of carbon 14 and carbon 13.

[0079] According to one embodiment, at least 80% of the carbon present in the biochar is biogenic, preferably at least 90%, more preferably at least 95%, advantageously at least 98%, more advantageously at least 99%.

[0080] Advantageously, 100% of the carbon present in biochar is biogenic.

[0081] The proportion of biogenic carbon in biochar is, for example, determined according to standard EN 16640, in particular standard EN 16640:2017. Advantageously, the biochar has a biogenic carbon content, measured according to standard EN 16640, ranging from 20% to 80% by mass, relative to the total mass of biochar, more preferably from 50% to 75% by mass.

[0082] Preferably, the biochar has an organic carbon content, measured according to ISO 9686, ranging from 1% to 60% by mass, more preferably from 2% to 50% by mass, typically from 3% to 45% by mass.

[0083] Preferably, the biochar has an inorganic carbon content, measured according to ISO 9686, ranging from 0.1% to 20% by mass, more preferably from 0.2% to 15% by mass, typically from 0.5% to 10% by mass. Preferably, the biochar has a graphitic carbon content, measured according to ISO 9686, ranging from 5% to 90% by mass, more preferably from 7% to 80% by mass, typically from 10% to 75% by mass.

[0084] Preferably, the biochar has a low nitrogen N content, more preferably less than or equal to 10% by mass, relative to the total mass of biochar, even more preferably ranging from 0.1% to 10% by mass, typically from 0.5% to 5% by mass.

[0085] Preferably, the biochar has a low phosphorus P content, more preferably less than or equal to 10% by mass, relative to the total mass of biochar, even more preferably ranging from 0.01% to 10% by mass, typically from 0.05% to 7.5% by mass.

[0086] Preferably, the biochar has a low potassium K content, more preferably less than or equal to 10% by mass, relative to the total mass of biochar, even more preferably ranging from 0.01% to 10% by mass, typically from 0.05% to 7.0% by mass.

[0087] Preferably, the biochar has a low calcium Ca content, more preferably less than or equal to 15% by mass, relative to the total mass of biochar, even more preferably ranging from 0% to 15% by mass, typically from 0.01% to 10% by mass.

[0088] Preferably, the biochar has a low magnesium Mg content, more preferably less than or equal to 10% by mass, relative to the total mass of biochar, even more preferably ranging from 0% to 10% by mass, typically from 0.1% to 3% by mass.

[0089] The content of nitrogen N, phosphorus P, potassium K, calcium Ca and / or magnesium Mg in the biochar is typically measured by elemental analysis. Preferably, the biochar has an oxygen O content, measured by elemental analysis, ranging from 0.1% to 50% by mass, relative to the total mass of biochar, more preferably ranging from 0.5% to 40% by mass, typically from 2% to 35% by mass.

[0090] Preferably, the biochar has a hydrogen content H, measured by elemental analysis, ranging from 0.01% to 20% by mass, relative to the total mass of biochar, more preferably ranging from 0.05% to 15% by mass, typically from 0.1% to 8% by mass.

[0091] According to one embodiment, the ratio between the mass of hydrogen present in the biochar and the total mass of organic carbon present in the biochar ranges from 0.01 to 5, preferably from 0.015 to 3, more preferably from 0.02 to 2.

[0092] According to one embodiment, the ratio between the mass of oxygen present in the biochar and the total mass of carbon (total carbon) present in the biochar ranges from 0.01 to 5, preferably from 0.02 to 3, more preferably from 0.04 to 1.

[0093] According to one embodiment, the biochar is porous, preferably of open porosity.

[0094] For the purposes of the invention, "open porosity" means that the pores of the material are connected to each other in such a way as to form a continuous network. All of the pores of the material are therefore accessible to water.

[0095] Preferably, the biochar has a porosity ranging from 10% to 90% by volume, more preferably from 30% to 85%, even more preferably from 50% to 85%.

[0096] Methods for measuring the porosity of a biochar are known to those skilled in the art. These include, in particular, the methods described in CE Brewer, BIOMASS AND BIOENERGY, 66, 2014, 176-185.

[0097] Advantageously, the biochar has a specific surface area, measured according to the BET method defined in the ISO 9277 standard, ranging from 1.5 m 2 / g at 500 m 2 / g, more preferably 5 m 2 / g at 450 m 2 / g, even more preferably 10 m 2 / g at 400 m 2 / g.Preferably, the biochar has a high pH, ​​typically greater than or equal to 5, more preferably ranging from 5 to 12, advantageously ranging from 6 to 10.

[0098] According to one embodiment, the biochar has a cation exchange capacity ranging from 1 cmol.Kg -1 at 100 cmol.Kg -1 , preferably 1.5 cmol.Kg -1 at 80 cmol.Kg -1 , more preferably 2 cmol.Kg -1 at 70 cmol.Kg -1 .

[0099] Methods for measuring the cation exchange capacity of a biochar are known to those skilled in the art. Examples include the Metson method and the Bower method.

[0100] According to one embodiment, the surface of the biochar is functionalized. Preferably, according to this embodiment, the surface of the biochar comprises at least one functional group chosen from: a phenol group, a lactone group (cyclic ester), a carboxylic acid group, a carboxylic anhydride group, a peroxide group, an amine group, a quinone group, a chromene group, an ether group, a pyrone group and any combination thereof.

[0101] The bituminous composition according to the invention preferably comprises from 0.1% to 50% by mass of biochar, relative to the mass of the bituminous composition, more preferably from 0.5% to 30%, even more preferably from 1% to 15%.

[0102] Plasticizing agent

[0103] The bituminous composition according to the invention further comprises at least one plasticizing agent.

[0104] For the purposes of the invention, the term "plasticizing agent" means a compound capable of reducing the Young's modulus, as well as the glass transition temperature of a material, so as to improve its cold properties, limit its brittleness, and increase its elongation at break.

[0105] The plasticizing agent is not specifically limited provided that it has the qualities required for the bituminous compositions of the invention. In particular, any plasticizing agent known to those skilled in the art and suitable for use in bitumens, in particular bitumen / polymer compositions, may be used.

[0106] According to a preferred embodiment, the plasticizing agent is chosen from: a) tall oil derivatives, b) plastic pyrolysis oils, c) triglycerides, and d) mixtures of a) and / or b) and / or c) and / or d).

[0107] Preferably, the bituminous composition according to the invention has a content of plasticizing agent(s) ranging from 0.1% to 30% by mass, preferably from 1% to 20% by mass, preferably from 2.5% to 10% by mass, relative to the total mass of the composition.

[0108] Preferably, the biochar(s) and the plasticizing agent are present in the bituminous composition of the invention in a mass ratio ranging from 10:1 to 1:10, more preferably from 5:1 to 1:5, even more preferably from 2:1 to 1:2, typically in a ratio of 1:1. a) tall oil derivatives

[0109] According to a first embodiment, the plasticizing agent is selected from tall oil derivatives. Crude tall oil (or CTO) is a by-product of the process of converting wood into paper pulp, also called the Kraft process. Distillation of crude tall oil yields a volatile and highly saturated fraction of long-chain fatty acids (mainly palmitic acid), called "tall oil heads". The next cut is tall oil fatty acids (or TOFA). This TOFA cut consists mainly of C18 and C20 fatty acids with varying degrees of unsaturation (e.g., oleic acid, linoleic acid, linolenic acid and various isomers thereof).Another cut, known as distilled tall oil (or DTO), is a mixture composed primarily of tall oil fatty acids and a smaller proportion of tall oil rosin. The next isolated tall oil rosin (or TOR) consists largely of a C19-C20 tricyclic monocarboxylic acid. The lower cut from the distillation is known as tall oil pitch (or simply "pitch").

[0110] Preferably, according to this embodiment, the plasticizing agent is obtained directly from tall oil, by simple distillation.

[0111] More preferably, the plasticizing agent is chosen from: crude tall oil, fractions of crude tall oil and mixtures of different fractions of tall oil.

[0112] Even more preferably, according to this embodiment, the plasticizing agent is chosen from “tall oil heads”, tall oil fatty acids (or TOFA for “Tall Oil Fatty Acids” in English), distilled tall oil (or DTO for “Distilled Tall Oil” in English), tall oil rosin (or TOR for “Tall Oil Rosin”) and tall oil pitch or tall oil pitch (in English “tall oil pitch” or simply “pitch”).

[0113] Even more preferably, the plasticizing agent is chosen from tall oil pitch or tall oil pitch (in English “tall oil pitch” or simply “pitch”).

[0114] Tall oil pitch, referenced under CAS No. 8016-81-7, is in the form of a complex mixture comprising mainly fatty acids such as palmitic acid, linoleic acid and oleic acid; fatty acid esters; resin acids such as abietic acid and its isomers, pimaric acid, isopimaric acid and sandaracopimaric acid; resin acid esters; diterpene alcohols; fatty alcohols and sterols.

[0115] Preferably, the tall oil pitch comprises:

[0116] - up to 30% by mass of free fatty acids,

[0117] - from 15% to 20% by mass of diglycerides,

[0118] - from 50% to 60% by mass of triglycerides, and

[0119] - from 10% to 15% by mass of sterols, compared to the total mass of the pitch.

[0120] Preferably, the tall oil pitch has an iodine index, measured according to standard NF EN ISO 3961, less than or equal to 100 g of I2 / 100 g of pitch, more preferably ranging from 70 to 100 g of I2 / 100 g of pitch, advantageously from 75 to 95 g of I2 / 100 g of pitch.

[0121] Preferably, the tall oil pitch has an acid number, measured according to standard NF EN ISO 660, less than or equal to 45 g of KOH / g of pitch, more preferably ranging from 10 to 40 g of KOH / g of pitch, advantageously from 10 to 35 g of KOH / g of pitch.

[0122] Preferably, according to this embodiment, at least 50% by mass of the plasticizing agent consists of tall oil derivatives, more preferably at least 60% by mass, more preferably at least 75% by mass, advantageously at least 80% by mass, more advantageously at least 90% by mass, typically at least 95% by mass.

[0123] More preferably, according to this embodiment, the plasticizing agent consists of tall oil derivatives. b) plastic pyrolysis oils

[0124] According to a second embodiment, the plasticizing agent is chosen from plastic pyrolysis oils.

[0125] For the purposes of the invention, the term "plastic pyrolysis oil" means a hydrocarbon product obtained by thermal conversion, in particular by pyrolysis, of plastics.

[0126] 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.

[0127] Common industrial methods for recycling hydrocarbons from plastic include thermal conversion liquefaction of plastic waste that might otherwise have ended up in a landfill or incinerator, followed by a purification step that includes hydrotreatment and contaminant removal using a variety of purification processes such as distillation.

[0128] Plastic waste can be liquefied, for example, by pyrolysis or hydrothermal treatment. The thermal conversion step transforms plastics and most of their additives and contaminants into gaseous chemicals, while most non-volatile contaminants or additives end up in the solid by-product, carbon, or ash. In principle, all types of plastic waste can be converted. However, a preliminary sorting step for non-organic waste is desirable. Purification of the output material is also necessary because several heteroelements (i.e., elements other than carbon, hydrogen, or oxygen) can be volatilized. 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 must be separated from each other before recycling. The main polymers found 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 other than the base 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 plastic manufacturing, e.g., halogens such as bromine in flame retardants, plasticizers, stabilizers, etc.

[0129] Silicone polymers, which are organic materials containing silicon, are often used in plastic formulations. Due to their surface characteristics, silicone applications 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 polymer modification.

[0130] In addition to these hetero-elements, used plastic waste may have been contaminated during its lifetime by remnants of liquids with which it has been in contact (beverages, personal care products, etc.) and food, which can also contaminate the plastic. Finally, some plastic waste may be present in the form of partially decomposed waste, such as partially burned plastic.

[0131] Finally, since plastics are contaminated with oxygenated compounds, plastic oils from pyrolysis liquefaction may also contain oxygenated compounds such as aldehydes or ketones. The oil from plastic pyrolysis can then be separated into several fractions by any type of separation process known per se:

[0132] • The light naphtha type cut with a distillation range between 50 and 200°C and a density between 720 Kg / m3 and 750 Kg / m3;

[0133] • 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;

[0134] • The heavy cut type VGO (“Vaccum Gasoil” in English) with a distillation interval between 300°C and 450°C and a density between 800 Kg / m3 and 840 Kg / m3;

[0135] • 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.

[0136] Preferably, the plasticizing agent is selected from the light cut of naphtha type, the medium cut of diesel type, the heavy cut of VGO type, the very heavy cut of VR type and any of their mixtures.

[0137] Preferably, according to this second embodiment, at least 50% by mass of the plasticizing agent consists of plastic pyrolysis oils, more preferably at least 60% by mass, even more preferably at least 75% by mass, advantageously at least 80% by mass, more advantageously at least 90% by mass, typically at least 95% by mass.

[0138] More preferably, according to this second embodiment, the plasticizing agent consists of plastic pyrolysis oils. c) triglycerides

[0139] According to a third embodiment, the plasticizing agent is chosen from triglycerides.

[0140] For the purposes of the invention, the term "triglycerides" means glycerides, i.e. esters of glycerol, the three alcohol functions of which have been esterified.

[0141] Preferably, the triglycerides are chosen from the compounds of the following formula (I): in which R1, R2 and R3 represent, independently, a hydrocarbon chain, linear or branched, saturated or unsaturated, comprising from 1 to 300 carbon atoms, and optionally one or more heteroatoms, preferably chosen from O and N.

[0142] Preferably, each of the groups R1, R2 and R3 independently comprises from 0 to 3 unsaturations.

[0143] Preferably, the groups R1, R2 and R3 represent, independently, a C1-C100, more preferably C2-C50, even more preferably C4-C36 hydrocarbon chain, optionally substituted by one or more heteroatoms, preferably chosen from O and N.

[0144] More preferably, the triglycerides of the invention are chosen from fatty acid triglycerides.

[0145] Preferably, the fatty acids are selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, ricinoleic acid, behenic acid, lignoceric acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, trans-vaccenic acid, linoleic acid, linoaidic acid, α-linolenic acid, γ-linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, eicosapentaenoic acid, clupanodonic acid, docosahexaenoic acid and mixtures thereof.

[0146] More preferably, the fatty acids are chosen from palmitic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, α-linolenic acid and mixtures thereof.

[0147] Even more preferably, the fatty acids are in the form of a mixture of palmitic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, and α-linolenic acid.

[0148] Advantageously, the fatty acids consist of a mixture comprising:

[0149] - 0.7% to 1.3% by mass of palmitic acid,

[0150] - from 0.9% to 1.2% by mass of stearic acid,

[0151] - from 2.8% to 5.5% by mass of oleic acid,

[0152] - from 84.2% to 94% by mass of ricinoleic acid,

[0153] - from 4.2% to 7.3% by mass of linoleic acid, and

[0154] - from 0.2% to 0.5% by mass of α-linolenic acid, relative to the total mass of fatty acids present in the triglycerides of the invention, in esterified form.

[0155] Triglycerides suitable for the invention are present in particular in animal fats, vegetable oils and dairy products.

[0156] Preferably, the triglycerides of the invention are of plant origin.

[0157] More preferably, the triglycerides of the invention are derived from castor oil. Preferably, according to this fourth embodiment, at least 50% by mass of the plasticizing agent consists of triglycerides, more preferably at least 60% by mass, more preferably at least 75% by mass, advantageously at least 80% by mass, more advantageously at least 90% by mass, typically at least 95% by mass.

[0158] More preferably, according to this third embodiment, the plasticizing agent consists of triglycerides. d) mixtures

[0159] The plasticizing agent of the invention may also consist of a mixture of the different compounds defined above. In particular, the plasticizing agent may consist of a mixture of tall oil derivatives and plastic pyrolysis oils, a mixture of tall oil derivatives and triglycerides, a mixture of plastic pyrolysis oils and triglycerides or a mixture of tall oil derivatives, plastic pyrolysis oils and triglycerides.

[0160] Elastomer(s)

[0161] According to one embodiment, the composition according to the invention further comprises at least one elastomer.

[0162] The elastomer is not particularly limited provided that it has the qualities required for the bituminous compositions of the invention.

[0163] Such elastomers are well known in the art and are generally rubbery polymers. In a preferred embodiment, the elastomer comprises styrene butadiene styrene (SBS), hydrogenated SBS, styrene isoprene styrene (SIS), styrene ethylene butadiene styrene (SEBS) and / or polyisobutadiene (PIB).

[0164] Preferably, the elastomer is typically selected from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene.

[0165] Preferably, the elastomer is chosen from block copolymers of formula S-BS, in which:

[0166] - each S, which may be identical or different, independently represents a block based on monovinyl aromatic hydrocarbon monomers,

[0167] - B represents a block based on butadiene monomers, said block B comprising pendant vinyl groups.

[0168] 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. A block is advantageously made up of the repetition of the same monomer.

[0169] In said block copolymers of formula SBS, the S blocks together represent at least 15 mol% of the total number of moles of monomeric units of the block copolymer. Said block copolymers have a weight-average molecular weight ranging from 40,000 to 500,000 g / mol and have a content of pendant vinyl groups contained in the B block, which is greater than or equal to 20 mol%, relative to the total number of moles of monomeric units of the block copolymer. These copolymers may be called, more simply, hereinafter, SBS elastomer. In general, the two S blocks of the heat-crosslinkable SBS elastomer are identical.

[0170] In the context of the invention, butadiene means 1,3-butadiene which is a conjugated diene. When butadiene, or more generally a conjugated diene, is polymerized via a 1,2-addition mechanism, the result is a vinyl group (also called a vinyl group) pendant relative to the backbone of the polymer. The pendant vinyl groups of the SBS block copolymer therefore correspond to the 1,2-addition polymerization of the conjugated diene monomers, and in particular of the majority butadiene monomers, within the B block. The units obtained by the polymerization of butadiene according to a 1,2-addition mechanism or according to a 1,4-addition mechanism have the same molar mass.

[0171] In particular, the monovinyl aromatic hydrocarbon monomer(s) present in the S blocks of the SBS heat-crosslinkable elastomer are chosen from 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 monomer according to the present invention is styrene, which is used, for the constitution of the S blocks as the sole monomer, or as the major monomer in mixtures with minor proportions of one or more other monomers such as o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, alpha methylstyrene, vinylnaphthalene, vinyltoluene and vinylxylene, namely, in proportions of at most 10% by mass, relative to the totality of the monovinyl aromatic hydrocarbon monomers present in said S blocks.The use of styrene as the sole monomer is particularly preferred in the present invention for the constitution of the S blocks of the SBS elastomer. Thus, the monovinylaromatic hydrocarbon monomers from which the S blocks of the SBS copolymers with thermally crosslinkable blocks are derived may be, independently, any monovinylaromatic hydrocarbon monomer as previously described and are preferably styrene.

[0172] The block B based on butadiene monomers entering into the composition of the mentioned block copolymers SBS is, preferably, solely composed of butadiene monomers, or of a mixture of butadiene comprising minor proportions of one or more other structurally related conjugated dienes, and in particular chosen from isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and 1,3-hexadiene, in particular representing at most 10% by mass, relative to the totality of the conjugated dienes present in the block B. Preferably, the monomers constituting the block B are exclusively butadiene monomers.

[0173] The SBS heat-crosslinkable block elastomer used in the context of the invention has a weight-average molecular mass Mw, ranging from 40,000 to 500,000 g / mol. Preferably, the SBS heat-crosslinkable block elastomer has a weight-average molecular mass Mw, 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 / mol and advantageously less than or equal to 150,000 g / mol.

[0174] Preferably, the SBS block copolymer used in the context of the invention has a weight-average molecular mass Mw greater than or equal to 50,000 g / mol, more preferably greater than or equal to 65,000 g / mol, even more preferably greater than or equal to 75,000 g / mol, and advantageously greater than or equal to 100,000 g / mol. According to particular embodiments, the SBS block copolymer has a weight-average molecular mass Mw in any range corresponding to the maximum and minimum values ​​mentioned above, and advantageously in the range from 100,000 to 150,000 g / mol.

[0175] As indicated above, the SBS block copolymer used in the context of the invention has a content of pendant vinyl groups greater than or equal to 5% by mole, relative to the total number of moles of monomeric units of the 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.

[0176] Preferably, the SBS block copolymer preferably has a content of pendant vinyl groups greater than or equal to 5% by mole, relative to the total number of moles of monomeric units of the SBS copolymer, preferably greater than or equal to 10%.

[0177] According to one embodiment, the SBS block copolymer preferably has a content of pendant vinyl groups less than or equal to 50 mol%, relative to the total number of moles of monomeric units of the SBS copolymer, more preferably less than or equal to 40 mol%, even more preferably less than or equal to 30 mol%, typically less than or equal to 20 mol%.

[0178] Advantageously according to this first embodiment, the SBS block copolymer has a content of pendant vinyl groups in any range corresponding to the maximum and minimum values ​​mentioned above, and advantageously in the range from 5% to 20% by mole.

[0179] According to a second embodiment, the SBS block copolymer used according to the invention preferably has a content of pendant vinyl groups greater than or equal to 25 mol%, relative to the total number of moles of monomeric units of the SBS copolymer, more preferably greater than or equal to 30 mol%.

[0180] Preferably, according to this second embodiment, the SBS block copolymer used according to the invention preferably has a content of pendant vinyl groups of less than or equal to 50 mol%, relative to the total number of moles of monomeric units of the SBS copolymer, more preferably less than or equal to 45 mol%. Advantageously according to this second embodiment, the SBS block copolymer has a content of pendant vinyl groups in any range corresponding to the maximum and minimum values ​​mentioned above, and advantageously in the range from 35% to 45 mol%.

[0181] Preferably, the pendant vinyl groups are distributed along the B block of the SBS polymer in a statistical manner. This characteristic results directly from the process used for the synthesis of the copolymer.

[0182] The number of moles of monomeric units of the S blocks present in the SBS block copolymer represents, together, at least 15% of the total number of moles of monomeric units of the SBS copolymer, preferably at least 16% by mole.

[0183] Preferably, the number of moles of monomeric units of the S blocks of the SBS polymer represents, together, from 15% to 50% by mole, relative to the total quantity of moles of monomeric units of the SBS block copolymer, 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. The number of moles of monomeric units of the S blocks of the SBS polymer can be determined by 13C NMR spectroscopy (Carbon Nuclear Magnetic Resonance).

[0184] Preferably, the content of monovinyl aromatic hydrocarbon monomer (advantageously styrene) of the SBS block copolymer, 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.

[0185] Preferably, the monovinyl aromatic hydrocarbon monomer (advantageously styrene) content of the SBS block copolymer, determined by NMR spectroscopy 13 C (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 SBS block copolymer.

[0186] Advantageously, SBS block elastomers are in an essentially non-hydrogenated form.

[0187] According to a particular embodiment, the block copolymer of formula SBS is obtained by coupling two block copolymers of formula S-B' in which the blocks S and B' are chosen to obtain an SBS block copolymer. The block B may therefore include a residue of a coupling agent, well known in the field in question. As examples of difunctional coupling agents, mention may be made of dibromoethane, diethyl adipate, divinylbenzene, dimethyldichlorosilane and methyl dichlorosilane.

[0188] Preferably, according to this particular embodiment, the efficiency of the coupling of the two block copolymers of formula S-B', 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%.

[0189] Examples of SBS block copolymers which can be used in the compositions according to the invention, as well as their preparation processes, are described in particular in patent US 5,798,401, as well as in document WO 2007 / 058994 and by the applicant in patent application WO 2011 / 013073.

[0190] It is possible that, in the bituminous compositions and the processes according to the invention, a single SBS block copolymer as described in the context of the invention is used, or that a mixture of SBS block copolymers as described in the context of the invention is used, or that one or more SBS block copolymer(s) as described in the context of the invention are used in combination with one or more other elastomers. According to a preferred variant, the matrix is ​​produced with only one or more, preferably a single, SBS elastomer. The latter preferably represents from 0.5 to 10% by mass, in particular from 1 to 6% by mass, and preferably from 1.5 to 4% by mass of the total mass of the bituminous composition. In the bituminous compositions according to the invention, said elastomer(s) is / are in a crosslinked form, but this does not affect the percentage that it / they represent within the composition.In other words, the percentages, before and after crosslinking, of the different components used for the preparation of the bituminous composition, are identical. When a mixture of elastomers, containing at least one elastomer other than the SBS elastomer as described in the context of the invention is used, the percentages of 0.5 to 10% by mass, in particular of 1 to 6% by mass, and preferably of 1.5 to 4% by mass given relative to the total mass of the bituminous composition, correspond to the total quantity of elastomers used (SBS + other elastomer(s)). In this case of use of a mixture of elastomers, containing at least one elastomer other than the SBS elastomers, the SBS elastomer represents at least 50%, preferably at least 70% by mass, and preferentially at least 90% of the total quantity of elastomers used (SBS + other elastomer(s)).

[0191] Preferably, the SBS elastomer(s) represent at least 80% by mass of the total quantity of elastomers, preferably at least 90% and preferentially at least 95% of the total quantity of elastomers present, if a mixture of elastomers is used to prepare the bituminous compositions according to the invention. In particular, it is possible for the mixture to contain a portion of S-B' used during the manufacture of the SBS elastomer by coupling, as explained previously.

[0192] 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 copolymer of monovinyl aromatic hydrocarbon and conjugated diene, in particular of copolymer of styrene and butadiene, relative to the mass of the bitumen / polymer composition (crosslinked).

[0193] According to one embodiment, the bitumen / polymer composition (optionally crosslinked) of the invention comprises from 1% to 8% 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 5% by mass.

[0194] 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.

[0195] Additives

[0196] According to one embodiment, the bituminous composition of the invention further comprises one or more additional additive(s).

[0197] These additional additives are known to those skilled in the art. 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. 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. 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. d) fluxes, 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. (e) anti-foam additives, in particular (but not limited to) chosen from polysiloxanes,oxyalkylated polysiloxanes and fatty acid amides derived from vegetable or animal oils. f) detergent additives and / or corrosion inhibitors, including (but not limited to) selected from the group consisting of amines, succinimides, alkenylsuccinimides, polyalkylamines, polyalkylpolyamines, polyetheramines and imidazolines. g) slip agents or anti-wear agents, including (but not limited to) selected from the group consisting of fatty acids and their ester or amide derivatives, including glyceryl monooleate, and mono- and polycyclic carboxylic acid derivatives. h) 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 maleic anhydride / alkyl (meth)acrylate copolymers obtainable by reacting a maleic anhydride / alkyl (meth)acrylate copolymer and an alkylamine or polyalkylamine having a hydrocarbon chain of 4 to 30 carbon atoms, preferably 12 to 24 carbon atoms; 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. i) antioxidants, for example of hindered phenolic type or of amino type, of alkylated para-phenylenediamine type. j) metal passivators. k) acidity neutralizers. l) additives for lowering the mixing temperature of asphalts and coated materials, those for improving the adhesion of bituminous binders to fillers and aggregates, such as, for example, polyisobutylene succinimides. m) acids, such as polyphosphoric acid, or diacids, in particular fatty diacids.,

[0198] 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.

[0199] 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.

[0200] Composition

[0201] Advantageously, the bituminous composition of the invention comprises, preferably consists essentially of, even more preferably consists (exclusively of):

[0202] - from 40% to 99.9% by mass of bitumen,

[0203] - from 0.1% to 50% by mass of biochar,

[0204] - from 0.1% to 30% by mass of plasticizing agent(s),

[0205] - optionally, from 0.1% to 20% by mass of one or more elastomer(s), preferably chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene, 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.

[0206] According to a first embodiment, the bituminous composition of the invention comprises, preferably consists essentially of, even more preferably consists (exclusively of):

[0207] - from 50% to 99% by mass of bitumen,

[0208] - from 0.5% to 30% by mass of biochar,

[0209] - from 1% to 20% by mass of plasticizing agent(s),

[0210] - optionally, from 1% to 8% by mass of one or more elastomer(s), preferably chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene

[0211] - optionally, from 0.5% to 5% by mass of additional additive(s) as described above, relative to the total mass of the bituminous composition.

[0212] Preferably, according to this first embodiment, the bituminous composition of the invention comprises, preferably consists essentially of, even more preferably consists (exclusively of):

[0213] - from 60% to 95% by mass of bitumen,

[0214] - from 1% to 15% by mass of biochar,

[0215] - from 2.5% to 10% by mass of plasticizing agent(s), and

[0216] - optionally, from 2% to 5% by mass of one or more elastomer(s), preferably chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene

[0217] - optionally, from 0.5% to 2.5% by mass of additional additive(s) as described above, relative to the total mass of the bituminous composition.

[0218] According to a second embodiment, the bituminous composition of the invention comprises, preferably consists essentially of, even more preferably consists (exclusively of):

[0219] - from 50% to 99% by mass of bitumen,

[0220] - from 0.5% to 30% by mass of biochar,

[0221] - from 2.5% to 20% by mass of plasticizing agent(s), and

[0222] - optionally, from 5% to 20% by mass of one or more elastomer(s), preferably chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene - optionally, from 0.5% to 5% by mass of additional additive(s) as described above, relative to the total mass of the bituminous composition.

[0223] Preferably, according to this second embodiment, the bituminous composition of the invention comprises, preferably consists essentially of, even more preferably consists (exclusively of):

[0224] - from 60% to 95% by mass of bitumen,

[0225] - from 1% to 15% by mass of biochar, and

[0226] - from 2.5% to 10% by mass of plasticizing agent(s),

[0227] - optionally, from 10% to 15% by mass of one or more elastomer(s), preferably chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene

[0228] - optionally, from 0.5% to 2.5% by mass of additional additive(s) as described above, relative to the total mass of the bituminous composition.

[0229] Preferably, the bituminous composition according to the invention is homogeneous. For the purposes of the invention, the term "homogeneous" means that the various components of the composition, namely the biochar(s), the plasticizing agent(s) and any elastomers and / or additives, are distributed uniformly in the bituminous matrix.

[0230] Preferably, the composition according to the invention has a penetrability at 25°C, measured according to standard EN 1426, ranging from 25 to 60 1 / 10 mm, more preferably from 30 to 50 1 / 10 mm.

[0231] Preferably, the composition according to the invention has a ring and ball softening temperature, measured according to standard EN 1427, greater than or equal to 55°C, more preferably greater than or equal to 60°C, advantageously ranging from 60°C to 80°C, typically ranging from 60°C to 75°C.

[0232] Preferably, the composition according to the invention has a threshold stress, measured according to standard NF EN 13587, less than or equal to 5 Mpa, more preferably less than or equal to 3.5 Mpa, advantageously ranging from 1 Mpa to 5 Mpa, typically ranging from 1.5 Mpa to 3 Mpa.

[0233] Preferably, the composition according to the invention has a maximum elongation stress, measured according to standard NF EN 13587, greater than or equal to 0.4 MPa, more preferably greater than or equal to 1 MPa, advantageously ranging from 0.4 MPa to 3 MPa, typically ranging from 0.8 MPa to 1.5 MPa. Preferably, the composition according to the invention has a threshold elongation, measured according to standard NF EN 13587, greater than or equal to 5%, more preferably greater than or equal to 10%, typically between 8% and 15%.

[0234] Preferably, the composition according to the invention has a maximum elongation, measured according to standard NF EN 13587, greater than or equal to 500%, more preferably greater than or equal to 550%, even more advantageously greater than or equal to 600%, typically from 550% to 650%.

[0235] Preferably, the composition according to the invention has an energy at 400%, measured according to standard NF EN 13587, greater than or equal to 20 J / cm 3 , more preferably greater than or equal to 21 J / cm 3 , advantageously ranging from 20 J / cm 3 at 50 J / cm 3 , typically ranging from 21 J / cm 3 at 30 J / cm 3 .

[0236] Preferably, the composition according to the invention has a total energy, measured according to standard NF EN 13587, greater than or equal to 2.5 J, more preferably greater than or equal to 2.75 J, advantageously ranging from 2.5 J to 10 J, typically ranging from 2.75 J to 5 J.

[0237] According to one embodiment, the composition of the invention comprises a significant proportion of bio-sourced, recycled or waste-derived materials. It can therefore have a high eco-material index. The eco-material index is defined by the following equation:

[0238] Eco-material index = 100% - [% of non-biosourced, non-biodegradable, non-recycled or non-waste materials], the percentages being expressed in mass, relative to the total mass of the composition.

[0239] According to one embodiment, the composition has an eco-material content of at least 5%, preferably at least 10%, preferentially at least 15%.

[0240] Advantageously, the bituminous composition of the invention has a content of biosourced compounds, measured according to standard ASTM D6866, greater than or equal to 5% by mass, relative to the total mass of the composition, preferably greater than or equal to 10% by mass, more preferably greater than or equal to 15% by mass.

[0241] For the purposes of the invention, the term "bio-based compounds" means a material derived at least in part from biomass resources. Biomass resources are organic materials available in a renewable or recurring manner, such as crop residues, wood residues, grasses and aquatic plants. Corn ethanol is a well-known example of a bio-based material derived from biomass resources. The content of bio-based material in a sample is typically determined by measuring the content of Carbon 14 (radioactive isotope of carbon) present in said sample.

[0242] Indeed, the method defined in the ASTM D6866 standard allows us to measure the traces of carbon-14 still present in a fossil. These traces of carbon-14 then make it possible to date the last moment when the molecules were absorbed (by ingestion or photosynthesis). This information is obtained by knowing the “half-life” time, which is the time it takes for half the quantity of the isotope initially present to disintegrate and disappear. This time is approximately 5,700 years, meaning that every 5,700 years, the quantity of carbon-14 decreases by half. We also conclude that if a dead plant contains half as much carbon-14 as a living plant, it must have been alive 5,700 years ago. Beyond 50,000 years, a sample contains almost no trace of the initial radioactive compound. If a laboratory measurement finds no remains in a fossil, it is certainly more than 50,000 years old.This is the case, for example, with oil and dinosaur bones.

[0243] Preferably, the bituminous composition of the invention has a carbon 14 content, measured according to standard ASTM D6866, greater than or equal to 4% by mass, relative to the total mass of the composition, preferably greater than or equal to 9% by mass, more preferably greater than or equal to 14% by mass.

[0244] Process for preparing a bituminous composition according to the invention

[0245] The bituminous compositions of the invention may be prepared by any method known to those skilled in the art. Generally, these methods comprise mixing the components and heating the resulting mixture. The bitumen may be heated before mixing. Usually, the bitumen is heated before mixing, and the additive(s) are added to the bitumen without having been heated beforehand. According to a particular embodiment of the invention, a bitumen composition is prepared by bringing into contact:

[0246] - at least one bitumen base;

[0247] - biochar, preferably as defined above;

[0248] - at least one plasticizing agent, preferably as defined above;

[0249] - possibly an elastomer as defined above;

[0250] - possibly one or more other additive(s), in particular one or more additional additive(s) as described above.

[0251] In particular, the mixing of the following components is carried out, under heating and stirring: - at least one bitumen base,

[0252] - biochar, preferably as defined above,

[0253] - at least one plasticizing agent, preferably as defined above,

[0254] - optionally an elastomer as defined above, chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene

[0255] - possibly one or more other additive(s), in particular one or more additional additive(s) as described above.

[0256] The mixture of bitumen, biochar, plasticizing agent, or even elastomer(s) and / or other additive(s) present, can be carried out at a temperature ranging from 90°C to 230°C, preferably from 120°C to 200°C, and preferentially from 150°C to 180°C.

[0257] Such a mixture is carried out under agitation, so as to facilitate the dispersion and good distribution of the biochar and the plasticizing agent, and possibly the elastomer, in the bitumen which will constitute the matrix of the composition, possibly in association with the additional additive(s). The conditions are adapted to lead to the obtaining of a homogeneous mixture and to the distribution of the biochar and the plasticizing agent (and the elastomer). Conventionally, the person skilled in the art will adjust the time and power of the agitation, as well as the mixing temperature, in particular depending on the bitumen, the precise nature of the biochar, the plasticizing agent and the elastomer when it is present to have a molten mixture. Advantageously, the mixing is carried out in such a way as to promote a good distribution of the biochar (and the elastomer) in the final bituminous composition obtained.

[0258] 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 biochar (and the elastomer) is, in general, carried out, while the bitumen is maintained at a temperature belonging to the range from 90 to 230°C, preferably to the range from 120 to 200°C, and preferentially to the range from 150 to 180°C.

[0259] The components can be introduced simultaneously or in sequence. Heating is maintained throughout the process, and the heating temperature can be modulated during the process. Agitation can be maintained or interrupted intermittently as needed, or modulated during the process.

[0260] According to particular embodiments, the method according to the invention comprises a homogenization step which makes it possible, in particular, to distribute the biochar (and the elastomer) 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 of 90 to 230°C, preferably to the range of 120 to 200°C, and preferably to the range of 150 to 180°C.

[0261] In the process according to the invention, one or more bitumen(s), one or more biochar(s), one or more plasticizing agent(s), optionally one or more elastomer(s), or even 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.

[0262] Of course, in the process, the quantities used of bitumen, biochar, plasticizing agent(s), or even elastomer(s) and / or additional additive(s) possibly present, 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.

[0263] 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 produce the quantities given for the description of the bituminous compositions according to the invention.

[0264] The bituminous compositions capable of being obtained by such processes also form an integral part of the invention.

[0265] Applications

[0266] 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.

[0267] The bituminous binder or bituminous composition according to the invention can in turn 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.

[0268] By bituminous mix is ​​meant a mixture of a bituminous binder with aggregates and possibly mineral and / or synthetic fillers. The bituminous mix comprises a bituminous binder according to the invention, and possibly mineral and / or synthetic fillers, preferably chosen from fines, sand, gravel and recycled millings. 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.

[0269] 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.

[0270] 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 an emulsion gravel. With regard to road applications, the invention also relates to asphalts as materials for manufacturing and covering pavements.

[0271] Asphalt means 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 consist of fines (particles with dimensions less than 0.063 mm), sand (particles with dimensions between 0.063 mm and 2 mm) and possibly gravel (particles with dimensions greater than 2 mm, preferably between 2 mm and 4 mm). Asphalts have 100% compaction and are mainly used to manufacture and cover sidewalks, whereas asphalts have a compaction of less than 100% and are used to manufacture roads. Unlike asphalts, asphalts are not compacted by roller during their installation.

[0272] 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.

[0273] Another aspect of the invention relates to the use of a bituminous composition in various industrial applications, in particular for preparing a waterproofing coating, a membrane or an impregnation layer. Industrial applications of the bituminous compositions include the manufacture of waterproofing membranes, noise-reducing membranes, insulation membranes, surface coverings, carpet tiles, impregnation layers.

[0274] The invention also relates to the use of the combination of at least one biochar and at least one plasticizing agent, preferably as defined above, in a bituminous composition, preferably in an optionally crosslinked bitumen / polymer composition, to reduce the carbon footprint of said composition.

[0275] For the purposes of the invention, the term "carbon footprint" of a product means the quantity of carbon (generally expressed in kg of CO2 equivalent per kg of product) required 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.

[0276] Preferably, the use of a combination of at least one biochar and at least one plasticizing agent as defined above makes it possible to reduce by at least 20% the carbon footprint of a bituminous composition, in particular a bitumen / polymer composition (crosslinked or not), compared to the same composition free of biochar and plasticizing agent, more preferably at least 30%, even more preferably at least 40%, advantageously at least 80%, more advantageously at least 90%, typically at least 95%, for example at least 98%. The values ​​expressed above are calculated considering that the bitumen at the end of its life is not burned and that the biogenic carbon present in the bitumen is not re-emitted.

[0277] The invention is illustrated by the following examples given without limitation.

[0278] EXAMPLES

[0279] 1. Materials and methods

[0280] In the examples below, the bituminous compositions were evaluated according to the following protocols:

[0281] - measurement of needle penetrability at 25°C (abbreviation: P25), according to standard EN 1426, the results being expressed in 1 / 10 mm,

[0282] - measurement of the ring-ball softening temperature (abbreviation: TBA), according to standard EN 1427, the results being expressed in °C,

[0283] - elastic return at 25°C (R25), expressed in %, according to standard EN 13398,

[0284] - mechanical properties (stress at maximum elongation, threshold elongation, maximum elongation, energy at 400%, total energy), measured according to standard NF EN 13587,

[0285] - the evaluation of the low temperature behavior of the compositions (BBR), according to standard EN 14771, by measuring the flexural rigidity modulus of the composition.

[0286] - aging acceleration protocol (PAV), according to standard NF EN 14769, conditions: 25 hours, 21 bars and 100°C. Raw materials

[0287] The compositions detailed below were prepared from the following raw materials:

[0288] Bitumen Base (B): grade 35 / 50 bitumen with a P25 penetrability of 40 1 / 10 mm and a TBA of 52°C, commercially available from TotalEnergies under the AZALT® brand;

[0289] SBS (E) heat-crosslinkable elastomer styrene / butadiene / styrene (SBS) block copolymer, comprising 30.5% by mass of styrene and 69.5% by mass of butadiene. The content of pendant vinyl groups resulting from the 1,2-addition polymerization of butadiene is 27.8% by mass relative to the total mass of copolymer. The copolymer has a weight-average molecular weight (Mw) of 142,500 Daltons and a polydispersity index Ip of 1.09. This copolymer is commercially available from the company KRATON under the name D1192;

[0290] Biochar: softwood biochar commercially available from the company TERRA FERTILIS;

[0291] Plasticizing agent: tall oil pitch, commercially available from KRATON under the reference TALL OIL PITCH PN;

[0292] Crosslinking agent: sulfur-rich agent

[0293] Additive: additive for trapping hydrogen sulfide emissions (in English “H2S scavenger”)

[0294] 2. Preparation of the compositions

[0295] Compositions C1*, C2* and C3 are prepared according to the following protocol:

[0296] The pure bitumen is first heated to 160°C in an oven, then transferred to a 3L reactor in which it is heated for 1 hour at 180°C.

[0297] The elastomer, and possibly the biochar and the plasticizing agent, are then added and the mixture ground for 30 min at 6000 rpm, still at 180°C, using a high shear rotorstator (Silverson).

[0298] The reactor is then placed under mechanical stirring at 400 rpm for 2 hours at 180°C.

[0299] This gives the thermo-crosslinked matrix of the bituminous composition.

[0300] The details of the compositions are given in Table 1 below. The contents are given by mass, relative to the total mass of the crosslinked bitumen / polymer composition. [Table 1]

[0301] Compositions C1* and C2* are comparative.

[0302] Compositions C3 are according to the invention. 3. Evaluations of the compositions

[0303] The properties of compositions C1*, C2* and C3 were evaluated according to the protocols defined above. The results are summarized in Table 2 below.

[0304] [Table 2]

[0305] It is observed that compositions C1*, C2* and C3 have equivalent properties. In particular, the compositions all have satisfactory properties, meeting the required technical specifications. By comparison between the results obtained for compositions C1* and C2*, it is observed that the incorporation of biochar in the bitumen / polymer matrix leads to a decrease in penetrability at 25°C and elastic recovery at 25°C, as well as to a deterioration in the cold performance (BBR) of the composition, before and after aging. These deteriorations are however not observed in the context of the composition

[0306] C3 according to the invention which further comprises the plasticizing agent. The incorporation of the plasticizing agent therefore makes it possible to compensate for the properties degraded by the integration of biochar. The composition of the invention thus has properties similar to those of the comparative composition C1, free of biosourced compounds.

Claims

CLAIMS 1. Bituminous composition comprising: - at least one bitumen base, - biochar, and - at least one plasticizing agent.

2. Bituminous composition according to claim 1, in which the plasticizing agent is chosen from: a) tall oil derivatives, b) plastic pyrolysis oils, c) triglycerides d) mixtures of a) and / or b) and / or c).

3. Bituminous composition according to claim 1 or claim 2, in which the biochar is derived from thermochemical conversion of biomass chosen from forest products; crop residues; animal waste; municipal waste and any of their mixtures.

4. Bituminous composition 'any one of claims 1 to 3, in which the biochar is derived from the thermochemical conversion of biomass chosen from hardwoods, in particular ash wood; cereal husks; nut shells, in particular cashew nuts; food waste; coffee grounds and any of their mixtures.

5. Bituminous composition according to any one of the preceding claims, having a biochar content ranging from 0.1% to 50% by mass, preferably from 0.5% to 30% by mass, preferably from 1% to 15% by mass, relative to the total mass of the bituminous composition.

6. 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.

7. Crosslinked bitumen / polymer composition, obtained by crosslinking, in particular chemical or thermal, of a bituminous composition according to claim 6.

8. Process for preparing a bituminous composition according to any one of the preceding claims, this process comprising: 1) bringing the following components into contact: at least one bitumen base, biochar, and at least one plasticizing agent 2) mixing the components.

9. Preparation process according to claim 8, wherein the mixing of the components is carried out under heating and stirring, preferably at a temperature ranging from 90°C to 230°C, more preferably from 120°C to 200°C, even more preferably from 150°C to 180°C.

10. Use of a bituminous composition according to any one of claims 1 to 7, 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.

11. Bituminous coating comprising a bituminous composition according to any one of claims 1 to 7, mixed with aggregates and / or recycled millings, and optionally mineral and / or synthetic fillers.

12. Asphalt comprising a bituminous composition according to any one of claims 1 to 7, mixed with mineral and / or synthetic fillers.

13. Waterproofing coating, preferably a membrane or an impregnation layer, comprising a bituminous composition according to any one of claims 1 to 7.

14. Use in a bituminous composition, in particular in an optionally crosslinked bitumen / polymer composition, of the combination of at least one biochar and at least one plasticizing agent, to reduce the content of compound(s) of fossil origin in said composition.

15. Use in a bituminous composition, in particular in an optionally crosslinked bitumen / polymer composition, of the combination of at least one biochar and at least one plasticizing agent, to reduce the carbon footprint of said composition.

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