EP3509735A1 - Method for manufacturing material in the form of granules that can be used as road binder or sealing binder and device for manufacturing same - Google Patents

Method for manufacturing material in the form of granules that can be used as road binder or sealing binder and device for manufacturing same

Info

Publication number
EP3509735A1
EP3509735A1 EP17780793.0A EP17780793A EP3509735A1 EP 3509735 A1 EP3509735 A1 EP 3509735A1 EP 17780793 A EP17780793 A EP 17780793A EP 3509735 A1 EP3509735 A1 EP 3509735A1
Authority
EP
European Patent Office
Prior art keywords
composition
bitumen
binder
drum
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP17780793.0A
Other languages
German (de)
French (fr)
Inventor
Soenke Schroeder
Mouhamad MOUAZEN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TotalEnergies Onetech SAS
Original Assignee
Total Marketing Services SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Total Marketing Services SA filed Critical Total Marketing Services SA
Publication of EP3509735A1 publication Critical patent/EP3509735A1/en
Pending legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/26Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic on endless conveyor belts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/20Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by expressing the material, e.g. through sieves and fragmenting the extruded length
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/10Making granules by moulding the material, i.e. treating it in the molten state
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10CWORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00Working-up pitch, asphalt, bitumen
    • C10C3/14Solidifying, Disintegrating, e.g. granulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/12Making granules characterised by structure or composition
    • B29B2009/125Micropellets, microgranules, microparticles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/16Auxiliary treatment of granules
    • B29B2009/163Coating, i.e. applying a layer of liquid or solid material on the granule

Definitions

  • the present invention relates to a method of manufacturing a material in divided form, solid at ambient temperature, which can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition, a clear binder.
  • a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition, a clear binder.
  • the material thus obtained has advantageous properties of resistance to compression and creep during its transport and / or storage at room temperature.
  • the process is economical and applicable on an industrial scale.
  • the invention also relates to a device for the manufacture of these materials.
  • bitumen used in construction, mainly for the manufacture of road pavements or in industry, for example for roofing applications. It is generally in the form of a highly viscous black material, even solid at room temperature, which becomes fluid upon heating.
  • bitumen In general, bitumen is stored and transported hot, in bulk, in tanker trucks or by boats at high temperatures in the range of 120 ° C to 160 ° C.
  • the storage and transport of hot bitumen has certain disadvantages.
  • the transport of hot bitumen in liquid form is considered dangerous and it is very framed from a regulatory point of view. This mode of transport presents no particular difficulties when the equipment and the transport infrastructures are in good condition. Otherwise, it can become problematic: if the tank truck is not sufficiently insulated, the viscosity of the bitumen may increase during a trip that is too long. Delivery distances for bitumen are therefore limited.
  • the maintenance of bitumen at high temperatures in tanks or tank trucks consumes energy. In addition, maintaining the bitumen at elevated temperatures for a long time may affect the properties of the bitumen and thus change the final performance of the bitumen.
  • bitumen in the form of granules transported and / or stored in bags, often used in places where the ambient temperature is high. These granules have the advantage of being easily manipulated.
  • pitches and bituminous compositions comprising them, clear binders, bitumen / polymer compositions, especially the stock solutions of bitumen / polymer compositions.
  • US 3,026,568 discloses a method of manufacturing bitumen granules coated with a powdery material, such as limestone powder.
  • the bituminous material is extruded through a nozzle into a spray tower. This process can only be carried out with mineral powders and in amounts not compatible with industrial production.
  • Another disadvantage lies in the fact that the coating of the granules can be achieved solely by dusting.
  • the application US 2011/0233105 describes solid asphalt at ambient temperature in the form of granules comprising a core and a coating layer, these granules being formed by extrusion through a die.
  • the document FR 2 998 896 describes a process for producing granules of bituminous composition.
  • the granules are formed by shear cutting. This method has the disadvantage that it can not be applied under economically satisfactory conditions to high quantities of materials.
  • No. 4,279,579 discloses an extrusion device making it possible, from a melt of material, to produce granules.
  • this document does not describe a specific use of this equipment for the production of granules of materials that can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition. , a clear binder.
  • EP 0 511 197 discloses an apparatus for extruding a fluid mass on a mobile support.
  • This apparatus comprises in particular a first fixed cylinder and a second cylinder arranged around the first cylinder and able to rotate around the first cylinder, the fluid mass placed in the first cylinder is extruded through nozzles on the surface of the second cylinder.
  • the document WO 2016/110747 describes a process for packaging bitumen in the form of pellets, characterized in that the bitumen is heated and then passed through a rotary cylinder perforated so as to form droplets of hot bitumen which are then cooled on a tread maintained at a temperature of 8 ° C to 10 ° C.
  • Document FR 2 765 229 discloses clear binders and bituminous binders which can be in the form of pellets or granules.
  • the Applicant has therefore sought to develop a process for producing granules of materials that can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition, a clear binder, in particular bitumen granules, capable of being subjected to high ambient temperatures without flowing, in particular materials, in particular bitumens, in the form of granules whose adhesion and agglomeration during their transport and / or storage and / or manipulation at high ambient temperature is reduced compared to the granules of the prior art.
  • An attempt has been made to develop a process that can be extrapolated to high quantities of material, which is economical, reproducible and can be implemented without difficulty on an industrial scale.
  • An object of the present invention is to provide a material that can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition, a clear binder, in particular a road bitumen. transportable and / or storable and / or manipulable at high ambient temperature, and whose properties are preserved over time.
  • the object of the present invention is to provide a material that can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition, in particular a road bitumen, transportable and / or storable for a period greater than 2 months, preferably 3 months, and at high ambient temperature, especially at a temperature below 100 ° C, preferably from 20 ° C to 80 ° C.
  • a material that can be used as a road binder or as a sealing binder such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition, in particular a road bitumen, transportable and / or storable for a period greater than 2 months, preferably 3 months, and at high ambient temperature, especially at a temperature below 100 ° C, preferably from 20 ° C to 80 ° C.
  • Another object of the invention is to provide a material that can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition, a clear binder, in particular a bitumen.
  • road easily manipulated, especially at elevated ambient temperature, in particular at a temperature up to 100 ° C, preferably from 20 ° C to 80 ° C.
  • the object of the present invention is to provide a material which can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition, a clear binder, in particular a road bitumen, easily handled after a transport and / or prolonged storage time at high ambient temperature, in particular during a transport and / or storage time longer than 2 months, preferably longer than 3 months, and at a temperature ranging from up to 100 ° C, preferably between 20 ° C and 80 ° C.
  • a material which can be used as a road binder or as a sealing binder such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition, a clear binder, in particular a road bitumen, easily handled after a transport and / or prolonged storage time at high ambient temperature, in particular during a transport and / or storage time longer than 2 months, preferably longer than 3 months, and at a temperature
  • An object of the present invention is to provide a material which can be used as a road binder or as a sealing binder, such as a road bitumen, pitch, mother solution for bitumen / polymer composition, a clear binder, in particular a road bitumen, in a form that allows it to flow in solid form at room temperature, so that it can be handled without loss of material.
  • a material which can be used as a road binder or as a sealing binder such as a road bitumen, pitch, mother solution for bitumen / polymer composition, a clear binder, in particular a road bitumen, in a form that allows it to flow in solid form at room temperature, so that it can be handled without loss of material.
  • a material which can be used as a road binder or as a sealing binder such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition, a clear binder, in particular a road bitumen, which is under a form that can be packaged in packaging, deconditioned, transferred to equipment, even at a high ambient temperature, without having to heat it, and without loss of material.
  • the material that can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition, in particular the proposed bitumen is in divided form and solid at ambient temperature in such a way that it solves satisfactorily the problems mentioned above.
  • Another objective is to propose an industrial and economic process for producing a material that can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition, a clear binder, in particular road bitumen, transportable and / or storable at ambient temperature.
  • a road binder or as a sealing binder such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition, a clear binder, in particular road bitumen, transportable and / or storable at ambient temperature.
  • Another object of the invention is to provide an industrial and economical process for manufacturing asphalt from transportable road bitumen and / or storable at ambient temperature.
  • Another objective of the invention is to propose an ecological and economical process for transporting and / or storing and / or handling a material that can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a solution mother for bitumen / polymer composition, a clear binder, in particular a road bitumen, at ambient temperature, making it possible to avoid the use of additional means for maintaining the temperature of said material during transport and / or storage and / or handling and to minimize the presence of waste and / or residues.
  • a material that can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a solution mother for bitumen / polymer composition, a clear binder, in particular a road bitumen, at ambient temperature
  • the invention relates to a process for producing a material which can be used as a road binder or as a sealing binder, solid at room temperature in the form of granules comprising a core based on a first composition and optionally a coating layer based on a second composition, the first composition comprising at least one material chosen from: a bitumen base, a pitch, a clear binder,
  • this process comprising the implementation of a device for granulation which comprises at least two coaxial drums and a horizontal tread: a fixed inner drum having at least one orifice and a rotating outer drum having a plurality of orifices, the drums being placed above an end of the tread, horizontal, driven by a speed V R , this method comprising at least:
  • the method further comprises, after step (iv) between steps (iv) and (v), a step (iv ') for cooling the drops of the first composition.
  • the cooling (iv ') is carried out by means of a temperature gradient on the tread.
  • the tread is conditioned at different temperatures over several sections (SI), ... (Si) of its course, with i an integer ranging from 2 to 8, preferably from 2 to 4 by thermal conditioning means.
  • the tread is conditioned at ambient temperature on a first section (SI) of its course, and at a temperature less than or equal to 20 ° C, preferably less than or equal to 15 ° C, on a second section S2.
  • SI first section
  • S2 second section
  • the ratio of the length of the first section (SI) to the length of the second section (S2) ranges from 25/75 to 75/25.
  • the rotary outer drum of the device comprises orifices having a diameter ranging from 2 to 10 mm, preferably from 2 to 8 mm, preferably from 3 to 7 mm, more preferably from 3.5 to 6 mm. .
  • the first composition in step (i) is brought to a temperature ranging from 100 to 270 ° C, preferably from 100 to 180 ° C, preferably from 120 to 160 ° C, even better from 130 to 150 ° C.
  • the speed V R of the tread is less than 4 m / min.
  • the method further comprises, after step (v), at least one step (vi) of drying the coated granules, preferably at a temperature ranging from 20 to 60 ° C., for a duration ranging from 5 minutes to 5 hours, preferably 5 minutes to 2 hours.
  • the material that can be used as a road binder or as a sealing binder is chosen from: a bitumen composition, a pitch, a clear binder, a bitumen / polymer stock solution, a clear binder / polymer stock solution .
  • the first composition comprises at least one material chosen from: a bitumen base, a pitch, a clear binder, a bitumen / polymer composition, a clear binder / polymer composition, a bitumen / polymer stock solution; a clear binder / polymer stock solution; a mixture of these materials.
  • the second composition comprises at least one anti-caking compound.
  • the anti-caking compound is chosen from: talc; fines generally of diameter less than 125 ⁇ , such as fine silicones, with the exception of fine limestones; sand such as fountain sand; cement ; carbon; wood residues such as lignin, lignosulphonate, conifer needle powders, conifer cone powders, especially pine powders; the ashes of rice balls; glass powder; clays such as kaolin, bentonite, vermiculite; alumina such as alumina hydrates; silica; silica derivatives such as silica fumes, functionalized silica fumes, in particular hydrophobic or hydrophilic silica fumes, pyrogenic silicas, especially hydrophobic or hydrophilic pyrogenic silicas, silicates, silicon hydroxides and silicon oxides ; plastic powder; lime; the plaster ; rubber crumb; polymer powder, such as styrene-butadiene copolymers (SB),
  • SB st
  • the second composition comprises at least 10% by weight of one or more viscosifiers relative to the total mass of the second composition.
  • the viscosifying compound has a dynamic viscosity greater than or equal to 50 mPa ⁇ s -1 , preferably from 50 mPa ⁇ s -1 to 550 mPa ⁇ s -1 , more preferably 80 mPa ⁇ s 1 at 450 mPa.s "1 , the viscosity being a Brookfield viscosity measured at 65 ° C.
  • the viscosifying compound is chosen from:
  • gelling compounds preferably of vegetable or animal origin, such as gelatin, agar-agar, alginates, cellulose derivatives, starches, modified starches and gellan gums; polyethylene glycols (PEG) such as PEGs having a molecular weight of between 800 gmol 1 and 8000 gmol 1 ;
  • PEG polyethylene glycols
  • the second composition comprises from 10 to
  • the second composition consists essentially of one or more anti-caking compounds.
  • the bitumen base has a needle penetration measured at 25 ° C according to the EN 1426 standard of 5 to 330 1/10 mm, preferably 20 to 220 1/10 mm.
  • the first composition further comprises at least one chemical additive chosen from: an organic compound, a paraffin, a polyphosphoric acid and their mixtures.
  • the first composition comprises:
  • the percentages being in mass relative to the total mass of the first composition.
  • the first composition has a ball and ring softening temperature (TBA) greater than or equal to 90 ° C, the TBA being measured according to the EN 1427 standard.
  • TBA ball and ring softening temperature
  • the first composition has a needle penetration measured at 25 ° C according to the EN 1426 standard of 5 to 45 l / 10mm.
  • the invention also relates to the use of the method as described above and below in detail, to produce a composition of material usable as a road binder or as a coating binder, solid at room temperature, which exhibits transport and storage at a temperature ranging from 20 to 80 ° C for a period greater than or equal to 2 months, preferably greater than or equal to 3 months.
  • the invention further relates to a device usable for carrying out a method as described above and below in detail, which comprises at least: a first cylindrical drum disposed above the tread and capable of rotation about a longitudinal axis, said first drum comprising a plurality of first passages through the periphery of the drum, a second coaxial cylindrical drum of the first drum, having means for longitudinally admitting in said second drum the mass to extrude and having on a portion of its wall a plurality of second passages directed towards the tread and radially aligned with said first passages, said wall portion being disposed adjacent to said first drum, said first drum being mounted to allow its rotation continues 360 ° about the longitudinal axis with respect to said second drum so that the relative rotation between said drums sequentially produces a misalignment and alignment of the first passages and second passages to allow the fluid mass to move radially outwardly through the aligned passages, and on the rolling, this device further comprising:
  • a reservoir in which an additive composition can be introduced the reservoir being connected to the injection channel through an injector and allowing a injecting the additive composition into the bitumen composition at the injection channel, located downstream of the reservoir and upstream of the double drum.
  • Figure 1 schematic representation of a device 1 according to the invention
  • Figure 2 sectional view of a part of the operation of the double drum 4 in the device 1 of the invention
  • FIG. 3 schematic representation in perspective of the reservoirs and material injection means of a device 1 according to the invention
  • compositions of material that can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for composition bitumen / polymer, a clear binder, in particular bitumen, by means of a particular granulation device, this device making it possible to form the core of the core / shell structures, under conditions which are reproducible, extrapolatable on a large scale, economical and provide granules having improved properties with respect to the granules of the same materials known from the prior art.
  • the expression "between X and Y" includes the terminals. This expression therefore means that the target range includes X, Y values and all values from X to Y.
  • Ambient temperature means the temperature resulting from the climatic conditions in which the material used as a road binder or as a sealing binder, in particular road bitumen, is transported and / or stored. More specifically, the ambient temperature is equivalent to the temperature reached during transport and / or storage of the material that can be used as a road binder or as a sealing binder, in particular road bitumen, it being understood that ambient temperature implies that no heat is not brought other than that resulting from climatic conditions.
  • the invention relates to materials which can be used as road binder or as sealing binder, in particular bitumens which may be subject to high ambient temperature, in particular a temperature of up to 100 ° C, preferably from 20 ° C to 80 ° C.
  • material usable as a road binder or as a sealing binder is meant in the sense of the present invention any material capable of being used for this purpose, and in particular: bitumen bases, bitumen / polymer compositions, compositions additivated bitumen, pitches, bitumen-polymer stock solutions, clear binders, light-polymer bonding stock solutions, mixtures of these materials in all proportions.
  • solid material at room temperature is meant a material having a solid appearance at ambient temperature whatever the transport and / or storage conditions. More specifically, solid material at ambient temperature is understood to mean a material which retains its solid appearance throughout transport and / or storage at ambient temperature, that is to say a material which does not flow at ambient temperature under its own weight and more, which does not flow when subjected to pressure forces from transport conditions and / or storage.
  • solid bitumen at ambient temperature is meant a bitumen having a solid appearance at ambient temperature regardless of the transport and / or storage conditions. More specifically, solid bitumen at ambient temperature is understood to mean a bitumen that retains its solid appearance throughout transport and / or storage at ambient temperature, that is to say a bitumen that does not flow at room temperature under its own weight and more, which does not flow when subjected to pressure forces from transport conditions and / or storage.
  • Coating layer covering all part of the surface of the core means that the coating layer covers at least 90% of the surface of the core, preferably at least 95% of the surface of the core, more preferably at least 99% of the surface of the heart.
  • the expression "essentially consists of" followed by one or more characteristics, means that may be included in the method or material of the invention, in addition to the components or steps explicitly listed, components or steps that do not significantly modify the properties and characteristics of the invention.
  • the method according to the invention makes it possible to obtain granules of material which can be used as road binder or as sealing binder, in particular solid bitumen, comprising a coating layer which is resistant to the climatic conditions and to the conditions of transport and / or storage of road binders and / or sealing binders, in particular which is resistant to climatic conditions and conditions of transport and / or storage of solid road asphalt, which breaks easily under a mechanical shear effect, such as for example under the effect of mechanical shear applied in a tank such as a kneader or kneading drum during the manufacture of asphalt.
  • the coating layer is resistant to the transport and / or storage of road binders and / or sealing binders, in particular bitumen, at room temperature in "Big Bags" while being brittle under the effect of mechanical shearing. It thus allows the liberation of the bitumen core during the manufacture of asphalt.
  • the method of the invention is implemented by means of a device which is shown in Figures 1 to 3 and which is illustrated by the production of a bitumen composition.
  • the process could be implemented, with simple adjustments of the parameters, to other compositions such as pitches, clear binders, stock solutions or mixtures of such compositions in all proportions.
  • This device 1 comprises a reservoir 11 equipped with heating means (not shown), and stirring means 13, for carrying the container of the reservoir 11, a bitumen composition 2, in the fluid state.
  • the first composition 2 is brought to a temperature chosen to avoid degrading said additives.
  • One or more injection channels 3 allow (the) transfer of the fluid bitumen composition 2 into the interior of the double pastillation drum 4.
  • the injection of bitumen composition 2 inside the double 4 as shown in FIG.
  • the device of the invention further comprises a reservoir 14 in which is placed an additive composition 15.
  • This reservoir 14 is connected to the injection channel 3 through an injector 16 and allows an injection of the additive composition 15 in the bitumen composition 2 at the channel 3, downstream of the tank 11 and upstream of the double drum 4.
  • certain additives degrade when they are stored hot in a bitumen composition and their introduction into the tank 11 would lead to their destruction before the bitumen composition 2 has reached the double pastillation drum 4.
  • Other additives decant on storage and lead to the formation of an inhomogeneous composition.
  • the pelletizing drum 4 comprises a fixed internal drum or stator 4B equipped with heating means (not shown) to maintain the composition 2, optionally additive, in the fluid state. It comprises a rotating outer drum 4A, the two drums being equipped with slots, nozzles and orifices allowing the pouring of bitumen drops 7 through the first fixed drum and the orifices 5 of the rotating outer drum. For example, as shown in FIG.
  • the first fixed drum 4B may comprise a longitudinal slot 5B and the second rotary drum 4A may have openings 5A of substantially identical size, regularly aligned, as illustrated in US Pat. No. 4,279,579. other arrangements of the orifices of the two drums are possible.
  • the drops 7 are regularly pelletized. through said orifices 5 and thus have substantially uniform sizes.
  • the drops of bitumen 7 are deposited on the upper face 6A of a tread 6, horizontal, driven by the rollers 12A and 12B, and one end of which is placed under the double drum 4.
  • the dimensions of the orifices 5 of the outer drum rotary control can control the size of the drops of bitumen 7.
  • the orifices 5A may consist of substantially circular orifices of diameter 4 mm.
  • the tangential velocity V T of the double drum 4 is parallel to the tread 6 and in the same direction as the speed V R of the tread 6.
  • the speed V R of the tread 6 is adapted to allow a deposit of the drops 7 regular and sufficiently distant from each other to prevent agglomeration or coalescence drops 7.
  • the tread 6 is equipped with a first thermal conditioning device 8 on a first section S1 of its length and a second thermal conditioning device 9 on a second section S2 of its length.
  • the packaging allows progressive cooling and solidification of the drops of bitumen 7.
  • the thermal conditioning means may consist of nozzles 8, 9 for vaporizing a fluid, such as water, on the underside 6B of the strip 6, at a chosen temperature.
  • a fluid such as water
  • the SI section over a length of 5 m conditions the tread 6 at room temperature (22-28 ° C), and the section S2, along a length of 5 m also, cools the tread to 20 m. ° C or at 15 ° C.
  • the tread 6 may be equipped with a larger number (for example 3, 4, 5, 6) of successive thermal conditioning devices so as to control the temperature of the tread 6, section by section, more finely.
  • the tread 6 may have any suitable dimensions to allow the deposition and gradual cooling of the drops of bitumen 7.
  • the tread 6 may have a length of 10 m and a width of 60 cm.
  • the dimensions of the tread 6 are adapted in particular according to the dimensions of the double drum 4 (width of the double drum 4 in particular), quantities of material to be treated, the desired temperature gradient.
  • the drops of bitumen 7 are transferred to receiving means 10 which may consist, for example, of a storage device, such as "big bags", coating, or a second tread allowing them to be transferred to treatment equipment such as bitumen drop coating equipment 7.
  • the drops of bitumen 7 are transferred to a coating device (not shown). ) such as a coating device by dipping, spraying or any other suitable device, depending on the chosen coating composition.
  • the drops of bitumen 7 are prepared from a first composition comprising at least one material chosen from: a bitumen base, a pitch, a clear binder, and mixtures thereof.
  • said first composition comprises at least one or more bitumen bases.
  • the method of the invention may comprise, after the step of depositing drops 7 on the tread 6 and before a possible step of coating, a step (iv ') for cooling the drops 7 of the first composition 2.
  • This cooling can be done by any means known to those skilled in the art such as storage at a low temperature, blowing cold air, ...
  • the method of the invention further comprises optionally coating the drops by the second composition. This coating may optionally be followed by drying the coated granules at a temperature ranging from 20 to 60 ° C, for a period ranging from 5 minutes to 5 hours, preferably from 5 minutes to 2 hours.
  • the mass ratio of the coating composition (second composition) relative to the mass of the first composition comprising the bitumen base, optionally additive, forming the core is from 0.1 to 1, preferably from 0.2 to 0.9.
  • the coating composition, or second composition comprises one or more anti-caking compounds.
  • the coating composition comprises at least one viscosifying compound and at least one anti-caking compound.
  • the viscosifying compound and the anti-caking compound are as described below.
  • These different coatings can be used whatever the chemical nature of the first composition, they are particularly suitable for bitumen compositions. If need be, the person skilled in the art knows how to adapt the second coating composition according to the nature of the first composition to produce an optimized result.
  • the material that can be used as a road binder or as a sealing binder, especially bitumen, solid at room temperature is conditioned in a divided form, that is to say in the form of small units, which are called granules or particles, comprising a core based on bitumen or pitch or clear binder, or a mixture these components (first composition) and optionally an envelope or shell or coating or coating layer or coating (second composition).
  • the granules of material that can be used as road binder or as sealing binder, in particular solid bitumen, according to the invention can have, within the same population of granules, one or more forms chosen from a cylindrical, spherical form. or ovoid.
  • the size of the granules is such that the longest average dimension is preferably 2 to 10 mm, preferably 2 to 8 mm, preferably 3 to 7 mm, more preferably 3.5 to 6 mm.
  • the size of the granules may vary according to the dimensions of the orifices of the rotary drum employed. Generally, all the orifices of the rotary drum are of substantially identical dimensions, however, it is possible to vary these dimensions.
  • the granules of material which can be used as road binder or as sealing binder, in particular bitumen, according to the invention have a weight of between 0.1 g and 50 g, preferably between 0.2 g and 10 g. more preferably between 0.2 g and 5 g.
  • the granules of material that can be used as a road binder or as a sealing binder are prepared from a first bitumen composition comprising one or more bitumen bases.
  • bitumen granules are prepared from a first bitumen composition comprising:
  • bitumen bases one or more bitumen bases
  • bitumen base and the chemical additive are as described below.
  • bitumen granules are prepared from a first bitumen composition comprising: one or more bitumen bases,
  • bitumen base from 0.5% to 20% by weight, preferably from 2% to 20% by weight, more preferably from 4% to 15% by weight of at least one anti-caking agent, the percentages being mass relative to the total mass of bitumen base.
  • the granules are prepared from a first composition comprising:
  • the percentages being in mass relative to the total mass of bitumen base.
  • the granules are prepared from a first composition comprising:
  • the percentages being in mass relative to the total mass of the first composition.
  • bitumen granules are prepared from a first road bitumen composition and covered with a second composition comprising at least one anti-caking agent.
  • This type of granules has a core / shell structure, also called core / coating layer.
  • the granules comprise, or better are essentially composed of: a heart prepared from a first composition,
  • a coating layer prepared from a second composition comprising at least one anti-caking compound.
  • bitumen granules are covered with anti-caking agent according to any known method, for example according to the process described in US Pat. No. 3,026,568.
  • bitumen granules are prepared from a first road bitumen composition and covered with a second composition comprising at least one anti-caking agent and at least one viscosifying agent.
  • the granules comprise, or better are essentially composed of:
  • a coating layer prepared from a second composition comprising at least one viscosifying compound and at least one anti-caking compound.
  • the different coating layers can be combined with all the variants of the first compositions.
  • the solid bitumen granules may further comprise one or more other coating layers, based on anti-caking agent covering all or part of the coating layer of the solid bitumen according to the invention. invention.
  • the granules of material that can be used as a road binder or as a sealing binder are prepared from a first composition comprising at least one pitch.
  • the granules consist of a first composition based on pitch.
  • the granules consist of a first composition based on pitch and at least one bitumen base.
  • the first composition comprises at least one pitch having a penetrability at 25 ° C ranging from 0 to 20 1/10 mm, a ball and ring softening temperature (TBA) ranging from 115 ° C at 175 ° C., it being understood that the penetrability is measured according to the EN 1426 standard and that the TBA is measured according to the EN 1427 standard.
  • the first composition comprises:
  • At least one chemical additive chosen from an organic compound, a paraffin, a polyphosphoric acid and their mixtures.
  • the first composition comprises:
  • the percentages being in mass relative to the total mass of the first composition.
  • the first composition comprises:
  • the first composition comprises:
  • the percentages being in mass relative to the total mass of the first composition.
  • the invention relates to pitch granules coated on at least a portion of their surface with an anti-caking agent as defined below, preferably over their entire surface.
  • the mass of anti-caking agent covering at least a portion of the surface of the pitch granules is between 0.2% and 10% by weight, preferably between 0.5% and 8% by weight, more preferably between 0.5% and 5% relative to the total mass of the pitch.
  • the mass of the anti-caking agent covering at least a portion of the surface of the pitch granules is about 1% by weight relative to the total mass of the pitch.
  • the anti-caking layer covering the pitch granules according to the invention is continuous so that at least 90% of the surface of said granules is covered with an anti-caking agent, preferably at least 95%, more preferably at least 99%.
  • the granules of material that can be used as road binder or as sealing binder are prepared from a first composition comprising at least one clear binder.
  • Colored coatings are increasingly used because they allow, among other things, to improve the safety of road users by clearly identifying specific routes such as pedestrian routes, bike paths, bus lanes. They also make it possible to materialize certain danger zones such as entrances to agglomeration or dangerous turns. Colored coatings promote visibility in low light conditions, for example at night or in particular sites such as tunnels. Finally, they simply improve the aesthetic appearance of urban roads and can be used for public squares, courtyards and schools, sidewalks, pedestrian streets, garden and park paths. , parking and rest areas.
  • the first composition comprises at least one clear binder.
  • the first composition comprises at least one clear binder base and at least one chemical additive chosen from an organic compound, a paraffin, a polyphosphoric acid and their mixtures.
  • the first composition comprises from 0.1% to 5% by weight, preferably from 0.5% to 4% by weight, more preferably from 0.5% to 2%, 8% by weight, and even more preferably from 0.5% to 2.5% by weight of said chemical additive relative to the total weight of said additivated clear binder.
  • the first composition comprises - at least one clear binder base
  • the first composition is called clear concentrated binder.
  • the granules are prepared from a first composition comprising:
  • the percentages being in mass relative to the total mass of the first composition.
  • cold solid binder and "split form” means a clear solid binder at room temperature which is packaged in a divided form, that is to say in the form of units which are distinct from one another and which are name granules.
  • the clear binder according to the invention is referred to indifferently in the present description "clear binder solid cold and divided form" or "clear binder additive".
  • the clear binder is a composition that can be used as a substitute for bitumen-based binders for the preparation, for example, of colored bituminous mix.
  • a clear binder is free of asphaltenes and can therefore keep the natural color of the granulate to which it is mixed or be easily colored with pigments.
  • the granules prepared from a first composition comprising at least one clear binder can be coated with a coating layer prepared from:
  • a second composition comprising at least one anti-caking compound, or
  • a second composition comprising at least one viscosifying compound and at least one anti-caking compound
  • the core or core of the solid bitumen granules according to the invention is prepared from a first composition, which is a road bitumen composition, said first composition being prepared by bringing into contact:
  • bitumen bases one or more bitumen bases
  • bitumen and “road bitumen” are used, in an equivalent manner and independently of one another.
  • Bitumen or “road bitumen” means any bituminous compositions consisting of one or more bitumen bases and optionally comprising one or more chemical additives, said compositions being intended for road application.
  • bitumen bases that may be used according to the invention, mention may first 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. .
  • the bitumen bases according to the invention are advantageously chosen from bitumen bases originating from the refining of crude oil.
  • the bitumen bases may be chosen from bitumen bases or bitumen base mixtures derived from the refining of crude oil, in particular bitumen bases containing asphaltenes or pitches.
  • the bitumen bases can be obtained by conventional processes for the manufacture of bitumen bases in a refinery, in particular by direct distillation and / or vacuum distillation of the oil.
  • bitumen bases may optionally be visbroken and / or deasphalted and / or rectified in air. It is vacuum distillation of atmospheric residues from atmospheric distillation of crude oil. This manufacturing process therefore corresponds to the succession of an atmospheric distillation and a distillation under vacuum, the feed supplying 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 charge usually composed of distillates and heavy products from the vacuum distillation of atmospheric residues from the distillation of petroleum. This method provides a base blown, or semi-blown or oxidized or rectified in air or rectified partially in air.
  • bitumen bases obtained by the refining processes can be combined with each other to obtain the best technical compromise.
  • the bitumen base can also be a bitumen base for recycling.
  • the bitumen bases may be bitumen bases of hard grade or soft grade.
  • production temperatures of between 100 ° C. and 270 ° C., preferably between 100 ° C. and 200 ° C., preferably between 140 ° C. and 200 ° C, more preferably between 140 ° C and 170 ° C, and stirring for a period of at least 10 minutes, preferably between 30 minutes and 10 hours, more preferably between 1 hour and 6 hours.
  • manufactured temperature means the heating temperature of the bitumen base (s) before mixing as well as the mixing temperature. The temperature and the duration of the heating vary according to the quantity of bitumen used and are defined by the standard NF EN 12594.
  • the blown bitumens can be manufactured in a blowing unit, by passing a stream of air and / or oxygen through a starting bituminous base.
  • This operation can be carried out in the presence of an oxidation catalyst, for example phosphoric acid.
  • the blowing is carried out at high temperatures, of 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 duration and the blowing temperature are adjusted according to the properties targeted for the blown bitumen and according to the quality of the starting bitumen.
  • the bitumen base used to manufacture the granules of the invention has a needle penetration measured at 25 ° C according to the EN 1426 standard of 5 to 330 1/10 mm, preferably 20 to 220 1 / 10 mm.
  • the so-called “needle penetration” measurement is carried out by means of a standardized test NF EN 1426 at 25 ° C. (P25). This characteristic of penetrability is expressed in tenths of a millimeter (dmm or 1/10 mm).
  • the needle penetration, 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.
  • the NF EN 1426 standard replaces the homologated NF T 66-004 standard of December 1986 with effect from December 20, 1999 (decision of the Chief Executive Officer of AFNOR dated November 20, 1999).
  • clear binder base compositions comprising a plasticizer, for example an oil of petroleum or plant origin, a structuring agent, for example a hydrocarbon resin, and a polymer.
  • a plasticizer for example an oil of petroleum or plant origin
  • a structuring agent for example a hydrocarbon resin
  • the composition of the clear binder bases determines certain essential properties of these binders, in particular the plasticity index, the viscosity of the binder, or the color which must be as clear as possible.
  • the clear binder base comprises:
  • plasticizing agent for example a natural or synthetic oil, free of asphaltenes
  • a structuring agent for example a hydrocarbon or vegetable resin, a copolymer,
  • doping agents or dopes, or dopants of adhesiveness.
  • Clear binder compositions are described in the following applications and patents and these clear binder compositions can be used as a clear binder base in the present invention.
  • a clear binder comprising hydrogenated white oils comprising at least 60% paraffinic carbons (according to the ASTM D2140 method) and a hydrocarbon resin, optionally mixed with copolymers of the ethylene-vinyl acetate (EVA) or low-density polyethylene type, for example of the EPDM (ethylene-propylene-diene-monomer) type, as described in WO 01/53409.
  • EVA ethylene-vinyl acetate
  • EPDM ethylene-propylene-diene-monomer
  • a clear binder comprising an oil with a naphthenic content between 35% and 80% and a hydrocarbon resin as described in EP 1783174 can be used as clear binder base.
  • a clear binder base a clear binder comprising a synthetic oil, a resin and an SBS or SIS type polymer can be used, as described in EP 1473327.
  • a clear binder base a clear binder may be used comprising:
  • At least one oil of petroleum origin preferably an aromatic oil comprising aromatic extracts of petroleum residues, obtained by extraction or dearomatization of residues of distillations of petroleum fractions,
  • At least one resin of plant origin preferably chosen from rosin esters, esters of glycerol and rosins, esters of pentaerythritol and rosins, taken alone or as a mixture, and
  • At least one latex preferably chosen from acrylic polymer latices, natural rubber latices and synthetic rubber latices, taken alone or as a mixture, as described in WO 2009/150519.
  • a clear binder base a clear synthetic binder can be used comprising:
  • At least one oil of vegetable origin preferably chosen from rapeseed, sunflower, soya, flax, olive, palm, castor oil, wood, corn, squash, grape seed oil , jojoba, sesame, walnut, hazelnut, almond, shea, macadamia, cotton, alfalfa, rye, safflower, peanut, coconut and copra, and mixtures thereof,
  • At least one resin of petroleum origin preferably chosen from resins of petroleum hydrocarbon origin resulting from the copolymerization of aromatic, aliphatic, cyclopentadienic petroleum fractions taken alone or as a mixture and
  • the clear binder base comprises:
  • a plasticizer consisting of an oil containing a total content of paraffinic compounds, measured according to ASTM D2140 method, of at least 50%, preferably at least 60% by weight, more preferably between 50%> and 90%, preferably between 60% and 80%, and
  • the oil is a synthetic oil derived from deasphalting unit cuts (or "DAO oil").
  • DAO oil synthetic oil derived from deasphalting unit cuts
  • the oil contains a total content of paraffinic compounds greater than or equal to 50%, preferably greater than or equal to 60% by weight, and a total naphthenic compounds content of less than or equal to 25% by weight, measured. according to ASTM Method D2140.
  • the oil contains a total content of paraffinic compounds greater than or equal to 50%, preferably greater than or equal to 60% by weight, a total naphthenic compounds content of less than or equal to 25% by weight, and total content of aromatic compounds of less than or equal to 25% by weight, measured according to the ASTM D2140 method.
  • the oil contains a total content of paraffinic compounds, measured according to the ASTM D2140 method, of between 50% and 90%, preferably between 60% and 80% by weight, a total content of naphthenic compounds included between 5% and 25% by weight, and a total content of aromatic compounds of between 5% and 25% by weight.
  • a total content of paraffinic compounds measured according to the ASTM D2140 method, of between 50% and 90%, preferably between 60% and 80% by weight, a total content of naphthenic compounds included between 5% and 25% by weight, and a total content of aromatic compounds of between 5% and 25% by weight.
  • the oil has an aniline point, measured according to the standard IS02977: 1997, greater than or equal to 80 ° C, preferably greater than or equal to 90 ° C, for example greater than 100 ° C.
  • the clear binder base preferably comprises (i) from 40 to 80% by weight of plasticizer, (ii) from 20 to 50% by weight of resin, (iii) from 1 to 7% by weight copolymer; and, (iv) optionally from 0.05% to 0.5% by weight of tackifier, for example amine, based on the weight of clear binder.
  • the clear binder base preferably comprises (i) from 40 to 80% by weight of plasticizer, (ii) from 20 to 50% by weight of resin, (iii) from 1 to 7% by weight of copolymer; and, (iv) from 0.05% to 0.5% by weight of tackifier, for example amine, based on the weight of clear binder base.
  • the clear binder base also comprises (i) from 45% to 70% by weight of plasticizer, (ii) from 25 to 50% by weight of resin, (iii) from 1% to 7% by weight of copolymer; and, (iv) optionally 0.1% and 0.3% by weight of tackifier, based on the total weight of clear binder base.
  • the clear binder base consists essentially of (i) from 40 to 80% by weight of plasticizer, (ii) from 20 to 50% by weight of resin, (iii) from 1 to 7% by weight of copolymer, based on the total weight of clear binder base.
  • the clear binder base consists essentially of (i) from 40 to 80% by weight of plasticizer, (ii) from 20 to 50% by weight of resin, (iii) from 1 to 7% by weight of copolymer and (iv) from 0.05% to 0.5% by weight of tackifier, based on the total weight of clear binder base.
  • the clear binder base essentially also consists of (i) from 45% to 70% by weight of plasticizer, (ii) from 25 to 50% by weight of resin (iii) of 1%) to 7% by weight of copolymer; and, (iv) 0.1% and 0.3% by weight of tackifier, based on the total weight of clear binder base.
  • the copolymer is a copolymer based on styrene and butadiene units which comprises a weight content of butadiene 1-2 ranging from 5 to 70%.
  • the copolymer is advantageously a copolymer based on styrene and butadiene units which comprises a weight content of butadiene 1-2 ranging from 5 to 70% and a weight content of 1,2-vinyl group of between 10 and 40. %.
  • said copolymer based on styrene and butadiene units has a weight average molecular weight of between 10,000 and 500,000, preferably between 50,000 and 200,000, and more preferably between 50,000 and 150,000 daltons.
  • a styrene / butadiene block copolymer or styrene / butadiene / styrene block copolymer will be used.
  • the clear binders according to the invention are advantageously characterized in that they have a color index of less than or equal to 4, preferably less than or equal to 3, as determined according to the ASTM DH4 scale.
  • they may advantageously have a Ball-Ring temperature softening temperature determined according to the NF EN 1427 standard of between 55 ° C. and 90 ° C.
  • the clear binder used according to the invention has a penetrability at 25 ° C., measured according to standard NF EN 1426, of between 10 and 220 1/10 mm, preferably between 30 and 100 1/10 mm, more preferably between 40 and 80 1/10 mm.
  • Those skilled in the art can modulate the penetrability of the clear binder used in the invention, in particular by judiciously choosing the weight ratio [structuring agent / plasticizer] in the composition of the clear binder base. Indeed, it is known that an increase in this ratio makes it possible to reduce the penetrability at 25 ° C.
  • the clear binder bases used in the invention may be prepared for example according to the following process comprising the steps of: (i) mixing the plasticizer, for example the oil DAO, and heating at a temperature between 140-200 ° C, for example from 10 minutes to 30 minutes,
  • steps (i) to (iv) can be changed.
  • the light binder granules further comprise at least one coloring agent as described above, such as for example a pigment.
  • the anti-caking agent and / or the coloring agent will be selected by those skilled in the art depending on the color of the desired clear binder.
  • pitch is a residue from the distillation of petroleum tars, oil, coal, wood or other organic molecules.
  • the invention relates here to the residues of petroleum distillation, also known as "petroleum pitch”.
  • the pitches can be obtained by conventional refinery manufacturing processes.
  • the manufacturing process corresponds to the succession of atmospheric distillation and vacuum distillation.
  • the crude oil is subjected to distillation at atmospheric pressure, which leads to the production of a gaseous phase, various distillates and an atmospheric distillate residue.
  • the residue of the atmospheric distillation is itself subjected to distillation under reduced pressure, called vacuum distillation, which makes it possible to separate a heavy gas oil, various sections of distillate and a distillation residue under vacuum.
  • This vacuum distillation residue contains "petroleum pitch” in varying concentration.
  • the vacuum distillation residue is subjected to a desalting operation by adding a suitable solvent, such as propane, which thus makes it possible to precipitate the pitch and to separate it from light fractions such as the unphased oil.
  • a suitable solvent such as propane
  • the vacuum distillation residue is subjected to a solvent extraction, and more precisely to furfural.
  • This heterocyclic aldehyde has the particularity of selectively solubilizing aromatic and polycyclic compounds. This process thus makes it possible to eliminate the aromatic extracts and to recover the "oil pitch”.
  • the pitch is an oxidized pitch.
  • the oxidized pitch according to the invention is obtained by oxidation of a mixture comprising pitch and a diluent, such as a light gasoline, also called “fluxing" subjected to an oxidation operation in a blowing tower. presence of a catalyst, at a fixed temperature and at a given pressure.
  • a diluent such as a light gasoline
  • oxidized pitches may be manufactured in a blowing unit, passing a stream of air and / or oxygen through a starting pitch.
  • This operation can be carried out in the presence of an oxidation catalyst, for example phosphoric acid.
  • the oxidation is carried out at high temperatures, of 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 duration and the oxidation temperature are adjusted according to the properties targeted for the oxidized pitch and according to the quality of the starting pitch.
  • the mechanical properties of pitches are generally appreciated by determining a series of mechanical characteristics by standardized tests, the most used of which are needle penetration expressed in 1/10 mm and the softening point determined by the ball and ring test. , also called ball and ring softening temperature (TBA).
  • the pitch exhibits needle penetration at 25 ° C. of 0 to 1/10 mm, preferably 0 to 1/10 mm, more preferably 0 to 10 1. / 10 mm, it being understood that the penetrability is measured according to standard EN 1426.
  • the pitch has a softening point of between 115 ° C and 175 ° C.
  • pitches used in the invention there are pitches respectively having a softening point between 115 ° C and 125 ° C, between 135 and 145 ° C or between 165 and 175 ° C.
  • plasticizing agent is meant in the sense of the invention, a chemical constituent for fluidizing and reducing the viscosity and the modulus of the binder obtained.
  • the plasticizing agent is chosen from oils of petroleum origin, oils of vegetable origin and their mixture.
  • the oils of plant origin are chosen from rapeseed, sunflower, soybean, flax, olive, palm, castor oil, wood, corn, squash, grape seed, jojoba, sesame, walnut, hazelnut, almond, shea, macadamia, cotton, alfalfa, rye, safflower, peanut, coconut and copra, and their mixtures.
  • the oils of vegetable origin are chosen from rapeseed, sunflower, linseed, coconut and soybean oils, and mixtures thereof.
  • oils of petroleum origin are chosen from aromatic oils or oils of synthetic origin.
  • the aromatic oils comprise aromatic extracts of petroleum residues, obtained by extraction or dearomatization of residues of distillations of petroleum fractions.
  • the aromatic oils have an aromatic content of between 30 and 95% by weight, preferably between 50 and 90% by weight, more preferably between 60 and 85% by weight (SARA method: Saturated / Aromatic / resins / asphaltenes).
  • the aromatic oils have a content of saturated compounds of between 1 and 20% by weight, advantageously between 3 and 15% by weight, more advantageously between 5 and 10% by weight (SARA method: Saturated / Aromatic / Resins / Asphaltenes).
  • the aromatic oils have a content of resin compounds of between 1 and 10% by weight, advantageously between 3 and 5% by weight, (SARA method: Saturated / Aromatic / Resins / Asphaltenes).
  • SARA method Saturated / Aromatic / Resins / Asphaltenes
  • the oils of synthetic origin come from distillation deasphalting cuts under reduced pressure (vacuum residue, RSV) of crude oil (hereinafter referred to as "DAO oil").
  • the plasticizer consists solely of a DAO oil.
  • the contents of paraffinic, naphthenic and aromatic compounds mentioned in the present application are determined according to the ASTM D2140 standard, in% by weight relative to the weight of the oil.
  • the plasticizer is an oil, for example a DAO oil, containing a total content of paraffinic compounds of at least 50% by weight, preferably at least 60% by weight, by weight. example between 50%> and 90%>, preferably between 60%> and 90%>, more preferably between 50%> and 80% and in particular between 55% and 70% or in particular between 60% and 75%. %.
  • the plasticizer is an oil, for example a DAO oil, further containing a total naphthenic compounds content of not more than 25%, for example between 5% and 25%, and in particular between 10% and 25%.
  • the plasticizer is an oil, for example a DAO oil, further containing a total aromatic content of not more than 25%, for example between 5% and 25%, and between 8% and 18%.
  • the plasticizer is an oil, for example a DAO oil, comprising the respective contents:
  • the plasticizer is an oil, for example a DAO oil, comprising the respective contents: (i) a total content of paraffinic compounds of between 60% and 75%;
  • DAO oil deasphalted oil
  • paraffin has a very low asphaltene content
  • evaporation temperature of between 440 ° C. and 750 ° C.
  • API gravity much higher than that vacuum residues.
  • paraffinic, naphthenic and aromatic compounds depend to some extent on the nature of the crude oil at the origin of the DAO oil and the refining process used.
  • Those skilled in the art can determine the respective contents of paraffinic, naphthenic and aromatic compounds of a DAO oil for example using the SARA fractionation method also described in Lee et al., 2014, Fuel Processing Technology 119: 204-210 and thus select the appropriate DAO oil for the preparation of the clear binder according to the invention.
  • the amount of plasticizer used in the process for preparing the clear binder base is 40% to 80%, preferably 45% to 70% by weight based on the weight total clear binder base.
  • the structuring agent The structuring agent
  • structural agent any chemical component imparting mechanical properties and satisfactory cohesiveness to said binder.
  • the structuring agent used in the context of the invention is a resin, preferably chosen from resins of petroleum hydrocarbon origin, for example derived from the copolymerization of aromatic, aliphatic, cyclopentadienic petroleum fractions, taken alone or as a mixture, preferably from aromatic oil couples.
  • resins of petroleum hydrocarbon origin for example derived from the copolymerization of aromatic, aliphatic, cyclopentadienic petroleum fractions, taken alone or as a mixture, preferably from aromatic oil couples.
  • it may be a thermoplastic resin polycycloaliphatic, for example hydrogenated cyclopentadiene homopolymers, low molecular weight.
  • the hydrocarbon resin of the cyclopentane type has a softening point (or Ball-Ring temperature, TBA, according to standard NF T 66-008) greater than 125 ° C., and a Gardner color number (according to the NF standard). T 20-030) equal to at most 1.
  • resins that can be used as structuring agents include, but are not limited to, resins of vegetable origin obtained from plants and / or plants. They can be called harvest, that is to say harvested from the living plant. They can be used as they are, we speak then of natural resins or be transformed chemically, one speaks then of modified natural resins.
  • the enhanced resins there are the enhanced resins, dammar, natural rosins, modified rosins, rosin esters and metal resinates. These can be taken alone or mixed.
  • Natural rosins include gem and wood rosin, especially pine, and / or tall oil. These natural rosins can be taken alone or as a mixture.
  • Modified rosins include hydrogenated rosins, disproportionated rosins, polymerized rosins and / or maleic rosins. These modified natural rosins can be taken alone or as a mixture, and undergo one or more disproportionation, polymerization and / or maleization treatments.
  • rosin esters mention may be made of the natural rosin methyl esters, the hydrogenated rosin methyl esters, the natural glycerol and rosin esters, the hydrogenated glycerol and rosin esters and the disubstituted glycerol and rosin esters, esters of glycerol and of polymerized rosins, esters of glycerol and of maleated rosin, esters of pentaerythritol and natural rosins and esters of pentaerythritol and hydrogenated rosins.
  • These rosin esters can be taken alone or as a mixture and come from rosins having undergone one or more disproportionation, polymerization and / or maleization treatment (s).
  • Esters of pentaerythritol and natural rosins and esters of pentaerythritol and hydrogenated rosins are the preferred rosin esters.
  • metal resinates there may be mentioned metal carboxylates, for example of Ca, Zn, Mg, Ba, Pb, Co, obtained from natural rosins or modified rosins.
  • Calcium resinates, zinc resinates, mixed calcium / zinc resinates, taken alone or as a mixture, are preferred.
  • the ratio by weight between the structuring agent and the plasticizer used for the preparation of the clear binder according to the invention is generally from 0.3 to 1.5, for example from 0.5 to 1 .
  • the amount of structuring agent used in the process for preparing the clear binder base is 25 to 50% by weight relative to the total weight of clear binder base.
  • the polymer used in the process for preparing the first composition is a copolymer based on conjugated diene units and monovinyl aromatic hydrocarbon units.
  • the conjugated diene is preferably chosen from those comprising from 4 to 8 carbon atoms per monomer, for example butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3- butadiene, 1,3-pentadiene and 1,2-hexadiene, chloroprene, carboxylated butadiene, carboxylated isoprene, especially butadiene and isoprene, and mixtures thereof.
  • the monovinyl aromatic hydrocarbon is preferably selected from styrene,
  • styrene ⁇ -methyl styrene, p-methyl styrene, p-tert-butyl styrene, 2,3-dimethyl styrene, p-methyl styrene, vinyl naphthalene, vinyl toluene, vinyl xylene, and the like or mixtures thereof, in especially styrene.
  • the polymer consists of one or more copolymers chosen from block copolymers of styrene and butadiene, styrene and isoprene, styrene and chloroprene, styrene and carboxylated butadiene or else styrene and isoprene. carboxyl.
  • a preferred copolymer is a copolymer based on butadiene units and styrene units such as SB styrene / butadiene block copolymer or SB SB styrene / butadiene / styrene block copolymer.
  • the styrene-conjugated diene copolymer in particular the styrene-butadiene copolymer, advantageously has a weight content of styrene ranging from 5 to 50%, preferably from 20 to 50% by weight.
  • the copolymer of styrene and conjugated diene in particular the styrene-butadiene copolymer, advantageously has a weight content of butadiene (1-2 and 1-4) ranging from 50 to 95%.
  • the copolymer of styrene and conjugated diene, in particular the styrene-butadiene copolymer advantageously has a content by weight of butadiene 1-2 ranging from 5 to 70%, preferably from 5 to 50%.
  • the 1,2-butadiene units are the units which result from the polymerization via the addition of 2-butadiene units.
  • the weight average molecular weight of the copolymer of styrene and of conjugated diene, and in particular that of the styrene-butadiene copolymer may be, for example, between 10,000 and 500,000, preferably between 50,000 and 200,000 and more. preferably from 50,000 to 150,000 daltons.
  • the total amount of polymer used in the process of the invention is 0.5 to 20% by weight, preferably 1 to 10%, preferably 1 to 7%, for example from 2% to 5% relative to the total weight of bitumen base base, or clear binder.
  • the total amount of polymer used in the process of the invention is 20% to 50% by weight, relative to the total weight of bitumen base, or in relation to the total mass. clear binder base.
  • the first composition is said mother solution of bitumen / polymer composition or parent solution of clear binder / polymer composition. It is intended to be transported and stored in concentrated form, then diluted with the desired amount of bitumen base or clear binder base just prior to its use as a road binder or as a coating binder.
  • the polymer is chosen from micronized polymers.
  • the polymer has particles of diameter ranging from 250 to 1000 ⁇ , preferably with a diameter ranging from 400 to 600 ⁇ .
  • the compatibilizing agent is chosen from waxes, for example animal waxes, vegetable waxes, mineral waxes and their mixtures.
  • Animal and vegetable waxes are mainly composed of mixtures of fatty acid derivatives (fatty acid esters) while mineral waxes are paraffinic derivatives.
  • the adhesiveness dopes are mainly composed of mixtures of fatty acid derivatives (fatty acid esters) while mineral waxes are paraffinic derivatives.
  • adhesiveness dopes may also be used in the first composition, mixed with the other components, in particular the clear binder, or the bitumen base or the pitch.
  • these are, for example, nitrogen-containing surfactant compounds derived from fatty acids (amines, polyamines, alkylpolymers, etc.).
  • the adhesiveness dopes When added to the first composition, the adhesiveness dopes generally represent between 0.05% and 0.5% by weight relative to the weight of light binder or bitumen base or pitch. For example, in a specific embodiment, from about 0.05% to about 0.5% amine, preferably from about 0.1% to about 0.3% amine, will be added to the mass. total base of clear binder or base bitumen or pitch.
  • the clear synthetic binder may also include one or more coloring agents, such as inorganic pigments or organic dyes.
  • the pigments are selected according to the color, the desired color for the coating.
  • metal oxides such as iron oxides, chromium oxides, cobalt oxides, titanium oxides will be used to obtain the colors red, yellow, gray, blue green or white.
  • Pigments can be added, indifferently in the clear binder or in the mix (mixed with the aggregates for example) or in an emulsion of the clear binder.
  • bitumen base or the light binder or the mixture of base bitumen and pitch may further comprise at least one chemical additive selected from: an organic compound, a paraffin, a polyphosphoric acid and mixtures thereof.
  • the solid material comprises at least one chemical additive
  • it is in an amount adapted so that its penetrability is preferably from 5 to 50 l / 10 mm and / or the ball and ring softening temperature (TBA) is preferably greater than or equal to 60 ° C, it being understood that the penetrability is measured at 25 ° C according to EN 1426 and the TBA according to EN 1427.
  • TBA ball and ring softening temperature
  • the chemical additive is an organic compound.
  • the organic compound has a molar mass less than or equal to 2000 gmol -1 , preferably a molar mass less than or equal to 1000 gmol -1 .
  • the organic compound is a compound of general formula (I):
  • Ar 1 and Ar 2 represent, independently of one another, a benzene ring or a fused aromatic ring system of 6 to 20 carbon atoms, substituted by at least one hydroxyl group, and
  • R represents an optionally substituted divalent radical, the main chain of which comprises from 6 to 20 carbon atoms and at least one group chosen from amide, ester, hydrazide, urea, carbamate and anhydride functions.
  • Ar 1 and / or Ar 2 are preferably substituted with at least one alkyl group of 1 to 10 carbon atoms, advantageously at one or more ortho positions with respect to the hydroxyl group (s), more preferably Ar 1 and Ar 2 are 3,5-dialkyl-4-hydroxyphenyl groups, advantageously 3,5-di-tert-butyl-4-hydroxyphenyl groups.
  • R is in the para position with respect to a hydroxyl group of Ar1 and / or Ar2.
  • the compound of formula (I) is 2 ', 3-bis [(3- [3, 5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide.
  • the organic compound is a compound of general formula (II):
  • the groups R and R ' which may be identical or different, contain a saturated or unsaturated, linear, branched or cyclic hydrocarbon-based chain comprising from 1 to
  • the X group contains a hydrocarbon chain, saturated or unsaturated, linear, cyclic or branched, comprising from 1 to 22 carbon atoms, optionally substituted, and optionally comprising hetero atoms, rings and / or heterocycles;
  • n and m are integers having a value of 0 or 1 independently of one another.
  • the groups R- (NH) n CONH and NHCO (NH) n -R ' are covalently linked by a CONH-NHCO hydrazide bond.
  • the group R, or the group R ' then comprises at least one group chosen from: a hydrocarbon chain of at least 4 carbon atoms, an aliphatic ring of 3 to 8 atoms, an aliphatic condensed polycyclic system, partially aromatic or entirely aromatic, each ring comprising 5 or 6 atoms.
  • the group R, the group R 'and / or the group X comprises at least one group chosen from: a hydrocarbon chain of at least 4 carbon atoms an aliphatic ring of 3 to 8 atoms, an aliphatic condensed polycyclic ring system, partially aromatic or wholly aromatic, each ring comprising 5 or 6 atoms.
  • the group R and / or R ' comprises an aliphatic hydrocarbon chain of 4 to 22 carbon atoms, in particular chosen from the groups C 4 H 9, C 5 H 11, C 9 H 19, C 11 H 23, C 12 H 25, C 17 H 35, C 18 H 37, C 21 H 43, C 22 H 45.
  • the group X represents a saturated linear hydrocarbon chain comprising from 1 to 22 carbon atoms.
  • the group X is chosen from the groups C2H4, C3H6.
  • the group X may also be a cyclohexyl group or a phenyl group, the radicals R- (NH) n CONH- and NHCO (NH) n -R'- may then be in the ortho, meta or para position. Moreover, the radicals R- (NH) n CONH- and NHCO (NH) n -R'- may be in the cis or trans position with respect to each other. In addition, when the radical X is cyclic, this ring may be substituted by groups other than the two main groups R- (NH) n CONH- and -NHCO (NH) n -R '.
  • the X group comprises two 6-carbon rings connected by a CH 2 group, these rings being aliphatic or aromatic.
  • the group X is a group comprising two aliphatic rings connected by an optionally substituted C3 ⁇ 4 group, for example:
  • the organic compound is a compound of general formula (II) chosen from derivatives hydrazides such as compounds C5H11- CONH-NHCO-C 1 5 Hi, C9H19-CONH-C9H19-NHCO, C iH 23 - CONH-NHCO-Ci iH 23, C 7 H 3 5 -CONH-NHCO-Ci7H 35 or C21H43-CONH-NHCO-C21H43; diamides such as N, N * -éthylènedi (stearamide) of the formula Ci 7 H 35 -CONH-CH 2 CH 2 -NHCO- Ci 7 H 35; and ureide derivatives such as 4,4'-bis (dodécylaminocarbonylamino) diphenylmethane of the formula C12H25-NHCONH- C6H4-CH2-C 6 H4-NHCONH-Ci2H2 5.
  • derivatives hydrazides such as compounds C5H11- CONH-NHCO-C
  • the compound of general formula (II) is chosen from those which satisfy the condition: the sum of the numbers of the carbon atoms of R, X and R 'is greater than or equal to 10, advantageously greater than or equal to 14, preferably greater than or equal to 18.
  • the compound of general formula (II) is chosen from those which satisfy the condition: the number of carbon atoms of at least one of R and R 'is greater than or equal to 10, advantageously greater than or equal to 12, preferably greater than or equal to 14.
  • the compound of general formula (II) is chosen from those of formula (IIA):
  • R, R ', m and X have the same definition as above.
  • the group X represents a saturated linear hydrocarbon-based chain containing from 1 to 22 carbon atoms, advantageously X represents a linear hydrocarbon-based saturated chain comprising from 1 to 12 carbon atoms more preferably from 1 to 4 carbon atoms.
  • the group X is chosen from C 2 H 4 and C 3 H 6 groups .
  • the compound of general formula (IIA) is chosen from those which satisfy the condition: the sum of the numbers of the carbon atoms of R, X and R 'is greater than or equal to 10, advantageously greater than or equal to 14, preferably greater than or equal to 18.
  • the compound of general formula (IIA) is chosen from those which satisfy the condition: the number of carbon atoms of at least one of R and R 'is greater than or equal to 10, advantageously greater than or equal to 12, preferably greater than or equal to 14.
  • the compound of general formula (IIA) is selected from the hydrazide derivatives such as C5H11-CONH- compounds NHCO-C 5 H n, CONH-C9H19-NHCO-C9H19, C11H23-CONH-NHCO-C11H23 C 7 H 35 -CONH-NHCO-C 17 H 35 , or C 2 H 43 -CONH-NHCO-C 2 H 43 ; diamides such as N, N * -éthylènedi (laurylamide) of formula CnH 23 -CONH-CH 2 -CH 2 -NHCO-CnH 3 i, N, N * -éthylènedi (myristylamide) of the formula Ci 3 H 27 - CONH-CH 2 -CH 2 -NHCO-Ci 3 H 27, N, N * -éthylènedi (palmitamide) of the formula H 3 Ci 5 i-CONH-CH 2 n, CONH-C9H
  • the compound of general formula (IIA) is N, N '-ethylenedi (stearamide) of formula C 7 H 35 -CONH-CH 2 -CH 2 -NHCO-C 17 H 35 .
  • the compound of general formula (II) is chosen from those of formula (IIB):
  • the sum of the numbers of the carbon atoms of R and R ' is greater than or equal to 10, advantageously greater than or equal to 14, preferably greater than or equal to 18.
  • the compound of general formula (II) is selected from derivatives hydrazides such as C5H11-CONH-C5H11-NHCO compounds, C9H19-CONH NHCO-C9H19, C iH 23 -CONH-NHCO-C n H 23, C 7 H 35 -CONH-NHCO-Ci 7 H 35, or C 2 iH 43 -CONH-NHCO-C 2 iH 43; diamides such as ⁇ , ⁇ '-ethylenedi (laurylamide) of formula C n H 23 -CONH-CH 2 -CH 2 -NHCO-C nH 3 i, ⁇ , ⁇ '-ethylenedi (myristylamide) of formula Ci 3 H 27 - CONH-CH 2 -CH 2 -NHCO-C 3 H 27 , N, N'-ethylenedi (palmitamide) of formula Ci 5 H 3 i-CONH-CH 2 -CH 2 -NHCO-Ci 5 H 3
  • the compound of general formula (II) is N, N * -ethylenedi (stearamide) of formula C 7 H 35 -CONH-CH 2 -CH 2 -NHCO-C 17 H 35 .
  • the chemical additive when the chemical additive is chosen from the organic compounds of formula (II), it is used in combination with at least one other chemical additive chosen from the organic compounds of formula (I), (III), (V) , (VI) and (VII) and / or the reaction products of at least one C3-C12 polyol and at least one C2-C12 aldehyde, in particular those comprising a group of formula (IV).
  • the organic compound is a compound of formula (III):
  • R and R ' which may be identical or different, contain a linear, branched or cyclic saturated or unsaturated hydrocarbon-based chain containing from 1 to 22 carbon atoms, which may be optionally substituted, and optionally comprising hetero atoms, rings and / or heterocycles,
  • Z represents a tri-functionalized group chosen from the following groups:
  • the compound of formula (III) is N 2, N 4, N 6 -tridecylmelamine having the following formula with R 'representing the group C 9 H 19:
  • R selected from the following groups, taken alone or in mixtures
  • the organic compound is a reaction product of at least one C 3 -C 12 polyol and at least one C 2 -C 12 aldehyde.
  • the polyols that may be used, mention may be made of sorbitol, xylitol, mannitol and / or ribitol.
  • the polyol is sorbitol.
  • the organic compound is a compound which comprises at least one function of general formula (IV):
  • R is chosen from a C 1 -C 11 alkyl, alkenyl, aryl or aralkyl radical, optionally substituted by one or more halogen atoms, or one or more C 1 -C 6 alkoxy groups.
  • the organic compound is advantageously a derivative of sorbitol.
  • sorbitol derivative is meant any reaction product, obtained from sorbitol.
  • any reaction product obtained by reacting an aldehyde with D-sorbitol. This condensation reaction produces sorbitol acetals, which are derivatives of sorbitol.
  • 1,3: 2,4-Di-O-benzylidene-D-sorbitol is obtained by reacting 1 mole of D-sorbitol and 2 moles of benzaldehyde and has the formula:
  • sorbitol derivatives may thus be all the condensation products of aldehydes, especially aromatic aldehydes with sorbitol. Sorbitol derivatives of general formula will then be obtained:
  • Ari and Ar 2 are optionally substituted aromatic rings.
  • the organic compound is a compound of general formula (V): R "- (COOH) z (V),
  • R represents a linear or branched, saturated or unsaturated chain comprising from 4 to 68 carbon atoms, preferably from 4 to 54 carbon atoms, more preferably from 4 to 36 carbon atoms, and z is an integer ranging from 2 to at 4.
  • the group R '' is preferably a saturated linear chain of formula C w H 2w with w an integer ranging from 4 to 22, preferably from 4 to 12.
  • the diacid is sebacic acid.
  • the diacids may also be diacid dimers of unsaturated fatty acid (s), that is to say dimers formed from at least one unsaturated fatty acid, for example from a single fatty acid. unsaturated or from two different unsaturated fatty acids.
  • the diacid dimers of unsaturated fatty acid (s) are conventionally obtained by intermolecular dimerization reaction of at least one unsaturated fatty acid (reaction of Diels Aid for example).
  • Preferably, only one type of unsaturated fatty acid is dimerized. They derive in particular from the dimerization of an unsaturated fatty acid, in particular C 6 to C 34, especially C 12 to C 22 , in particular C 16 to C 20 , and more particularly C 18 .
  • a preferred fatty acid dimer is obtained by dimerization of linoleic acid, which can then be partially or fully hydrogenated.
  • Another preferred fatty acid dimer is obtained by dimerization of methyl linoleate. In the same way, it is possible to find triacids of fatty acids and tetracides of fatty acids, obtained respectively by trimerization and tetramerization of at least one fatty acid.
  • the organic compound is a compound of general formula (VI):
  • the groups Y and Y ' represent, independently of one another, an atom or a group chosen from: H, - (CH 2 ) q -CH 3 , - (CH 2 ) q -NH 2 , - (CH 2 ) q- OH, - (CH 2 ) q-COOH or
  • the organic compound is a compound of general formula (VII): R-NH-CO-CO-NH-R '(VII)
  • R and R ' which may be identical or different, represent a saturated or unsaturated, linear, branched or cyclic hydrocarbon-based chain comprising from 1 to 22 carbon atoms, preferably from 8 to 12 carbon atoms, which may be substituted, and comprising optionally heteroatoms, rings and / or heterocycles.
  • the chemical additive is a paraffin.
  • Paraffins have chain lengths of 30 to 120 carbon atoms (C 30 to C 20).
  • the paraffins are advantageously chosen from polyalkylenes.
  • polymethylene paraffins and polyethylene paraffins will be used according to the invention. These paraffins may be of petroleum origin or come from the chemical industry.
  • paraffins used are synthetic paraffins resulting from the conversion of biomass and / or natural gas.
  • these paraffins contain a large proportion of so-called "normal" paraffins, that is straight-chain, unbranched linear paraffins (saturated hydrocarbons).
  • the paraffins may comprise from 50 to 100% of normal paraffins and from 0 to 50% of isoparaffins and / or branched paraffins. More preferably, the paraffins comprise 85 to 95% of normal paraffins and 5 to 15%) of isoparaffins and / or branched paraffins.
  • the paraffins comprise from 50 to 100% of normal paraffins and from 0 to 50% of isoparaffins. Even more preferably, the paraffins comprise from 85 to 95% of normal paraffins and from 5 to 15% of isoparaffins.
  • the paraffins are polymethylene paraffins. More particularly, paraffins are synthetic paraffins of polymethylene, for example paraffins resulting from the conversion of synthesis gas by the Fischer-Tropsch process. In the Fischer-Tropsch process, paraffins are obtained by reaction of hydrogen with carbon monoxide on a metal catalyst. Fischer-Tropsch synthesis methods are described for example in the publications EP 1 432 778, EP 1 328 607 or EP 0 199 475.
  • the chemical additive is a polyphosphoric acid.
  • the polyphosphoric acids (PPA) that can be used in the invention are described in WO 97/14753. These are compounds of the formula PqHrOs in which q, r and s are positive numbers such that:
  • q> 2 and in particular q is from 3 to 20 or more and that 5q + r-2s 0.
  • polyphosphoric acids may be linear compounds of formula P q H (q + 2) O (3q + 1) corresponding to the structural formula:
  • All these polyphosphoric acids can be considered as polycondensation products by heating aqueous metaphosphoric acid. It will not be departing from the scope of the invention by combining several different chemical additives such as various organic compounds of formula (I), (II), (III), (V), (VI) and (VII), the products of reacting at least one C3-C12 polyol and at least one C2-C12 aldehyde, in particular those comprising a group of formula (IV), and / or different paraffins and / or various polyphosphoric acids in the bitumen base.
  • chemical additives such as various organic compounds of formula (I), (II), (III), (V), (VI) and (VII), the products of reacting at least one C3-C12 polyol and at least one C2-C12 aldehyde, in particular those comprising a group of formula (IV), and / or different paraffins and / or various polyphosphoric acids in the bitumen base.
  • the first composition comprising a bitumen base, of which the core of the granules is composed comprises from 0.1% to 10% by weight, preferably from 0.5% to 5% by weight. mass, more preferably 0.5%) to 2.5% by weight of chemical additive relative to the total mass of the first composition.
  • the first composition comprises at least two chemical additives.
  • the first composition comprises at least one first chemical additive of formula (V) and at least one second chemical additive chosen from: chemical additives of formula (I); chemical additives of formula (II); chemical additives of formula (III); chemical additives of formula (V); chemical additives of formula (VI); the chemical additives of formula (VII) and the reaction products of at least one C 3 -C 12 polyol and at least one C 2 -C 12 aldehyde, in particular those comprising a group of formula (IV), the second chemical additive being distinct from the first chemical additive.
  • second chemical additive chosen from: chemical additives of formula (I); chemical additives of formula (II); chemical additives of formula (III); chemical additives of formula (V); chemical additives of formula (VI); the chemical additives of formula (VII) and the reaction products of at least one C 3 -C 12 polyol and at least one C 2 -C 12 aldehyde, in particular those comprising a group of formula (IV), the second chemical additive being distinct from the first chemical additive.
  • the first composition comprises at least one first chemical additive of formula (V) and at least one second chemical additive of formula (II).
  • the first composition comprises at least one first additive of formula (V) and at least one second chemical additive of formula (IIA).
  • the first composition comprises at least one first chemical additive of formula (II) and at least one second chemical additive chosen from: chemical additives of formula (I); chemical additives of formula (II); chemical additives of formula (III); chemical additives of formula (V); chemical additives of formula (VI); the chemical additives of formula (VII) and the reaction products of at least one C 3 -C 12 polyol and at least one C 2 -C 12 aldehyde, in particular those comprising a group of formula (IV), the second chemical additive being distinct from the first chemical additive.
  • second chemical additive chosen from: chemical additives of formula (I); chemical additives of formula (II); chemical additives of formula (III); chemical additives of formula (V); chemical additives of formula (VI); the chemical additives of formula (VII) and the reaction products of at least one C 3 -C 12 polyol and at least one C 2 -C 12 aldehyde, in particular those comprising a group of formula (IV), the second chemical additive being distinct from the first chemical additive.
  • the first chemical additive of formula (II) is chosen from the chemical additives of formula (IIA).
  • the first composition comprises at least one first chemical additive of formula (IIA) and at least one second chemical additive chosen from: chemical additives of formula (I); chemical additives of formula (IIB); chemical additives of formula (III); chemical additives of formula (V); chemical additives of formula (VI); the chemical additives of formula (VII) and the reaction products of at least one C 3 -C 12 polyol and at least one C 2 -C 12 aldehyde, in particular those comprising a group of formula (IV), the second chemical additive being distinct from the first chemical additive.
  • second chemical additive chosen from: chemical additives of formula (I); chemical additives of formula (IIB); chemical additives of formula (III); chemical additives of formula (V); chemical additives of formula (VI); the chemical additives of formula (VII) and the reaction products of at least one C 3 -C 12 polyol and at least one C 2 -C 12 aldehyde, in particular those comprising a group of formula (IV), the second chemical additive being distinct from the first chemical additive
  • the first composition comprises at least one first additive of formula (IIA) and at least one second additive of formula (V).
  • the first chemical additive of formula (II) is N, N'-ethylenedi (stearamide).
  • the first composition comprises at least sebacic acid or 1,10-decanedioic acid and at least N, N'-ethylenedi (stearamide).
  • the first composition comprises at least one first additive of formula (I) and at least one second chemical additive chosen from: chemical additives of formula (I); chemical additives of formula (II); chemical additives of formula (III); chemical additives of formula (V); chemical additives of formula (VI); the chemical additives of formula (VII) and the reaction products of at least one C 3 -C 12 polyol and at least one C 2 -C 12 aldehyde, in particular those comprising a group of formula (IV), the second chemical additive being distinct from the first chemical additive.
  • second chemical additive chosen from: chemical additives of formula (I); chemical additives of formula (II); chemical additives of formula (III); chemical additives of formula (V); chemical additives of formula (VI); the chemical additives of formula (VII) and the reaction products of at least one C 3 -C 12 polyol and at least one C 2 -C 12 aldehyde, in particular those comprising a group of formula (IV), the second chemical additive being distinct from the first chemical additive.
  • the second chemical additive is chosen from the chemical additives of formula (II) and the chemical additives of formula (V).
  • the second chemical additive of formula (II) is chosen from the chemical additives of formula (II A).
  • the second chemical additive of formula (II) is N, N'-ethylenedi (stearamide).
  • the second chemical additive of formula (V) is sebacic acid or 1,10-decanedioic acid.
  • the first chemical additive of formula (I) is 2 ', 3-bis [(3- [3, 5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide.
  • the mass ratio of the first chemical additive with respect to the second chemical additive is from 1: 99 to 99: 1, preferably from 1: 9 to 9: 1, even more preferably from 1: 5 to 5: 1.
  • the first composition may further comprise at least one olefinic polymer adjuvant.
  • the olefin polymer adjuvant is preferably selected from the group consisting of (a) ethylene / glycidyl (meth) acrylate copolymers; (b) ethylene / monomer A / monomer B terpolymers and (c) copolymers resulting from the grafting of a monomer B onto a polymer substrate.
  • the ethylene / glycidyl (meth) acrylate copolymers are advantageously chosen from random or block copolymers, preferably random copolymers of ethylene and a monomer chosen from glycidyl acrylate and glycidyl methacrylate, comprising from 50% to 99.7% by weight, preferably from 60% to 95% by weight, more preferably 60% to 90% by weight of ethylene.
  • the terpolymers are advantageously chosen from random or sequential terpolymers, preferably random, of ethylene, a monomer A and a monomer B.
  • the A monomer is selected from vinyl acetate and alkyl acrylates or methacrylates to C 6.
  • Monomer B is selected from glycidyl acrylate and glycidyl methacrylate.
  • the ethylene / monomer A / monomer B terpolymers comprise from 0.5% to 40% by weight, preferably from 5% to 35% by weight, more preferably from 10% to 30% by weight of units derived from monomer A, and from 0.5% to 15% by weight, preferably from 2.5% to 15% by weight of units derived from monomer B, the remainder being formed from units derived from ethylene.
  • the copolymers result from the grafting of a B monomer selected from glycidyl acrylate and glycidyl methacrylate onto a polymeric substrate.
  • the substrate polymer consists of a polymer chosen from polyethylenes, in particular low-density polyethylenes, polypropylenes, statistical or block copolymers, preferably random copolymers of ethylene and vinyl acetate, and random or sequential copolymers, preferably random copolymers, of ethylene and alkyl acrylate or methacrylate to C 6, comprising from 40% to 99.7% by weight, preferably 50%> 99% by weight of ethylene.
  • Said graft copolymers comprise from 0.5% to 15% by weight, preferably from 2.5% to 15% by weight of grafted units derived from monomer B.
  • the olefinic polymer adjuvant is chosen from among the random terpolymers of ethylene (b), of a monomer a chosen from acrylates or methacrylates of alkyl to C 6 and a monomer B selected from glycidyl acrylate and glycidyl methacrylate, comprising 0.5% at 40% by weight, preferably from 5% to 35% by weight, more preferably from 10% to 30% by weight of units derived from monomer A and, from 0.5% to 15% by weight, preferably from 2%, 5% to 15%) by weight of units derived from monomer B, the remainder being formed from units derived from ethylene.
  • the first composition comprising the bitumen base, of which the core of the granules is composed, comprises from 0.05% to 15% by weight, preferably from 0.1% to 10% by weight. % by weight, more preferably from 0.5% to 6% by weight of the olefinic polymer adjuvant, relative to the total weight of the first composition.
  • the first composition may also comprise other known additives or other known bitumen elastomers such as copolymers SB (block copolymer of styrene and butadiene), SBS (block copolymer). styrene-butadiene-styrene), SIS (styrene-isoprene-styrene), SBS * (star styrene-butadiene-styrene block copolymer), SBR (styrene-b-butadiene rubber), EPDM (modified ethylene propylene diene).
  • copolymers SB block copolymer of styrene and butadiene
  • SBS block copolymer
  • SIS styrene-isoprene-styrene
  • SBS * star styrene-butadiene-styrene block copolymer
  • SBR styrene-b-butadiene
  • the first composition comprises a combination of the chemical additive of formula (II) and the olefinic polymer adjuvant described above.
  • olefinic polymer adjuvant is selected from the (b) ethylene / monomer A / monomer B terpolymers described above is also preferred.
  • the anti-caking compound is a mixture of the anti-caking compound:
  • anti-caking compound is of mineral or organic origin.
  • anti-caking agent or “anti-caking compound” is meant any compound which limits, reduces, inhibits, delays, the agglomeration and / or the adhesion of the granules together during their transport and / or their storage. at room temperature and which ensures their fluidity during handling.
  • the anti-caking compound is chosen from: talc; fines, also called “fibers", generally of diameter less than 125 ⁇ , such as fine silicones, with the exception of fine limestones; sand such as fountain sand; cement ; carbon; wood residues such as lignin, lignosulphonate, conifer needle powders, conifer cone powders, especially pine powders; the ashes of rice balls; glass powder; clays such as kaolin, bentonite, vermiculite; alumina such as alumina hydrates; silica; silica derivatives such as silica fumes, functionalized silica fumes, in particular hydrophobic or hydrophilic silica fumes, pyrogenic silicas, especially hydrophobic or hydrophilic pyrogenic silicas, silicates, silicon hydroxides and silicon oxides ; plastic powder; lime; the plaster ; rubber crumb; polymer powder, such as styrene-butadiene copolymers
  • the anti-caking agent is chosen from talc; the fines generally of diameter less than 125 ⁇ with the exception of fine limestones, such as siliceous fines; wood residues such as lignin, lignosulphonate, conifer needle powders, conifer cone powders, especially pine powders; glass powder; sand such as fountain sand; silica fumes, especially hydrophobic or hydrophilic silica fumes; and their mixtures.
  • the anti-caking compound is chosen from silica fumes.
  • the compounds "silica fume” and “fumed silica” have the same chemical definition and are registered under the same CAS number 112 945-52-5. Therefore, in the sense of the invention can be used these compounds indifferently from one another
  • fumed silica is meant either a fumed silica or a fumed silica derivative.
  • silica is meant a compound obtained by the vapor phase hydrolysis of chlorosilanes such as silicon tetrachloride, in a flame of oxygen and hydrogen. Such methods are generally referred to as pyrogenic processes whose overall reaction is: S1CI 4 + H 2 + O 2 ⁇ SiO 2 + 4 HCl. Pyrogenic silicas are distinguished from other silicon dioxides in that they have an amorphous structure. High purity (> 99.8% silica), they have a low hydrophilic character (no microporosity).
  • the fumed silica compound is fumed silica.
  • the fumed silica compound has a specific surface area of between 25 and 420 m 2 / g, preferably between 90 and 330 m 2 / g, more preferably between 120 and 280 m 2 / g.
  • SA surface area
  • the fumed silica compound has an average particle size of between 5 and 50 nm.
  • the fumed silica compound has a pH of between 3 and 10 when in the aqueous phase. According to one embodiment of the invention, the fumed silica compound has a carbon content of between 0.1 and 10% by weight relative to the total weight of the fumed silica compound.
  • the fumed silica compound is selected from a hydrophilic fumed silica compound, a hydrophobic fumed silica compound and mixtures thereof.
  • the fumed silica compound is a hydrophilic fumed silica compound.
  • hydrophilic is meant a compound that is miscible with water in all proportions.
  • the fumed silica compound, or fumed silica derivative, used within the meaning of the invention may be chemically modified.
  • silanized fumed silicas as described in WO 2004/020532, or in WO 2007/128636,
  • hydrophilic pyrogenic silicas as described in WO 2009/071467, WO 2011/000133 filed in the name of Degussa AG or Degussa Gmbh,
  • silica fumes made hydrophobic by treatment with polysiloxanes as described in WO 2008/141932, or by silanization as described in WO 2008/141930,
  • the fumed silica compound can be used alone or as a mixture in a coating composition.
  • the fumed silica compound can be used in the process according to the invention in the form of a powder or in dispersion in a solvent which evaporates after application.
  • the composition comprises at least one fumed silica compound and at least one solvent
  • the composition comprises from 5 to 70% by weight of fumed silica compound relative to the total weight of the composition, more preferably from 20 to 40% by weight.
  • the solvent is an organic solvent or water.
  • organic solvent is meant any solvent immiscible with a bitumen, such as an alcohol, for example ethanol.
  • the compounds of fumed silica used in the invention are commercially available and for example may be sold by Evonik Degussa under the tradename Aerosil ® such as Aerosil ® 200 the, by Cabot Corporation under the Cab-O-Sil ® and CAB-O-SPERSE ® or by Wacker Chemie AG under the brand name HDK ® .
  • the mass of the fumed silica compound covering at least a portion of the surface of the granules is between 0.2% and 10% by weight, preferably between 0.5% and 8% by weight, more preferably between 0.5% and 5% relative to the total mass of the first composition.
  • the granules of the first composition are covered with the fumed silica compound according to any known method, for example according to the process described in US Pat. No. 3,026,568.
  • the core of the granules further comprises at least one fumed silica compound as defined above.
  • the core of the granules of the first composition further comprises between 0.5% and 20% by weight, preferably between 2% and 20% by weight, more preferably between 4% and 15% by weight of the composition. fumed silica compound with respect to the total mass of the first composition.
  • viscosifier and “viscosifying compound” are used in the sense of the invention, in an equivalent manner and independently of one another.
  • viscosifier or “viscosifying compound” is meant a compound which has the property of decreasing the fluidity of a liquid or a composition and thus increasing its viscosity.
  • the viscosifier within the meaning of the invention is a material which has a dynamic viscosity greater than or equal to 50 mPa ⁇ s "1, preferably 50 mPa.s" 1-550 mPa.s “ more preferably from 80 mPa.s "1 to 450 mPa.s “ 1 , the viscosity being a Brookfield viscosity measured at 65 ° C.
  • the viscosity of a viscosifier according to the invention is measured at 65 ° C. by means of a Brookfield CAP 2000+ viscometer and at a rotation speed of 750 rpm. The measurement is read after 30 seconds for each temperature.
  • the viscosifier is chosen from:
  • gelling compounds preferably of vegetable or animal origin, such as: gelatin, agar-agar, alginates, cellulose derivatives, starches, modified starches, or gellan gums;
  • PEG polyethylene glycols
  • PEG- 1 polyethylene glycols
  • 800 a PEG having a molecular weight of 800 gmol -1
  • 800 a PEG having a molecular weight of 1000 gmol -1
  • PEG-1500 a PEG having a molecular weight of 1500 g mol -1 (PEG-1500)
  • PEG-6000 polyethylene glycols
  • the viscosifier is chosen from:
  • gelling compounds preferably of vegetable or animal origin, such as: gelatin, agar-agar, alginates, cellulose derivatives or gellan gums;
  • PEG polyethylene glycols
  • PEG- 1 polyethylene glycols
  • 800 a PEG having a molecular weight of 800 gmol -1
  • 800 a PEG having a molecular weight of 1000 gmol -1
  • PEG-1500 a PEG having a molecular weight of 1500 g mol -1 (PEG-1500)
  • PEG-6000 polyethylene glycols
  • the coating layer :
  • the coating layer is obtained by applying a composition (second composition) comprising at least one anti-caking compound on all or part of the core surface of the granules, in particular bitumen. solid.
  • a composition comprising at least one anti-caking compound on all or part of the core surface of the granules, in particular bitumen. solid.
  • the coating layer consists essentially of one or more anti-caking compounds.
  • the mass of the anti-caking compound covering at least a portion of the surface of the granules is 0.2% to 20% by weight, preferably 0.5% to 20%> in bulk, preferably from 2% to 20% by weight, more preferably from 4% to 15% by weight relative to the total mass of the granule cores, in particular of the bitumen base of the granules.
  • the mass of the fumed silica compound covering at least a portion of the surface of the granules is between 0.2% and 10%. %> by weight, preferably between 0.5%> and 8% by weight, more preferably between 0.5% and 5% relative to the total weight of the first composition.
  • the coating layer is obtained by applying a composition (second composition) comprising at least one viscosifying compound and at least one anti-caking compound on all or part of the surface of the core. granules, in particular solid bitumen.
  • the coating layer, formed from the second composition is solid at ambient temperature, including at elevated ambient temperature.
  • the second composition comprising at least one viscosifying compound and at least one anti-caking compound has a viscosity greater than or equal to 200 mPa.s -1 , preferably between 200 mPa.s -1 and 700 mPa.s. 1 , the viscosity being Brookfield viscosity.
  • the second composition comprises at least 10% by weight of at least one viscosifying compound relative to the total mass of the second composition, preferably from 10 to 90% by weight, more preferably from 10 to 85% by weight. .
  • the second composition comprises from 10 to 90% by weight of viscosifying compound relative to the total weight of the second composition, preferably from 15 to 85%), even better from 15 to 60%.
  • the second composition comprises from 10 to 90% by weight of anti-caking compound relative to the total weight of the second composition, preferably from 15 to 85%. even better from 40 to 85%.
  • the vicosifant is a PEG, such as for example
  • the second composition comprises from 10 to 90% by weight of viscosifying compound relative to the total mass of the second composition, preferably from 40 to 90%, even better 60 to 90%.
  • the vicosifant is a PEG, such as for example
  • the second composition comprises from 10 to 90% by weight of anti-caking compound relative to the total mass of the second composition, preferably from 10 to 60%, more preferably from 10 to 40%.
  • the second composition comprises at least 10% by weight of an anti-caking compound relative to the total mass of the second composition, preferably from 10 to 90% by weight, more preferably from 15 to 90% by weight. mass.
  • the coating layer represents at least 5% by weight relative to the total mass of the granule, preferably from 10 to 60% by weight, more preferably from 10 to 50%.
  • the second composition forming the coating layer may optionally comprise one or more compounds chosen from: chemical additives, polymers, etc.
  • the viscosifying compound and the anti-caking compound represent at least 90% by weight relative to the total mass of the second composition forming the coating layer, more preferably at least 95% by weight and advantageously at least 98% by weight. .
  • the second composition essentially consists of the viscosifying compound and the anti-caking compound.
  • the granules of material, preferably bitumen, solid obtained by the process of the invention can be used as road binder.
  • the road binder can be used to manufacture mixes, in combination with aggregates according to any known method.
  • the granules of solid material at room temperature according to the invention are used for the manufacture of asphalt.
  • Bituminous mixes are used as materials for the construction and maintenance of pavement bodies and their pavement, as well as for the realization of all road works. For example, superficial coatings, hot mixes, cold mixes, cold mixes, low emulsions, base layers, binding, hooking and rolling, and other combinations of a bituminous binder and road aggregate having particular properties, such as anti-rutting layers, draining asphalts, or asphalts (mixture between an asphalt binder and sand-like aggregates).
  • the granules of solid material, in particular solid bitumen obtained by the method of the invention can be implemented in a process for the manufacture of mixes comprising at least one road binder and aggregates, the road binder being chosen from among the granules of solid material, in particular bitumen according to the invention, this process comprising at least the steps of:
  • a tank such as a kneader or a kneading drum
  • the method of the invention has the advantage of being able to be implemented without prior step of heating the granules of solid material, in particular solid bitumen.
  • the asphalt manufacturing process does not require a step of heating the granules of solid material, in particular solid bitumen before mixing with the aggregates because, in contact with the hot aggregates, the solid material, especially solid bitumen at ambient temperature, melts.
  • the solid material, in particular the ambient-temperature solid bitumen obtained by the process according to the invention as described above, has the advantage of being able to be added directly to the hot aggregates, without having to be melted before mixing with the hot aggregates. .
  • the step of mixing the aggregates and road binder is carried out with stirring, then the stirring is maintained for at most 5 minutes, preferably at most 1 minute to allow to obtain a homogeneous mixture.
  • the solid material, in particular solid bitumen, in the form of granules obtained according to the method of the present invention is remarkable in that it allows the transport and / or storage of solid material, in particular road bitumen, at ambient temperature in optimum conditions, in particular without there being agglomeration and / or adhesion of the solid material, especially solid bitumen, during its transport and / or its storage, even when the ambient temperature is high.
  • the coating layer of the granules breaks under the effect of contact with hot aggregates and shear and releases the first composition, especially the bitumen base.
  • the presence of the coating layer in the road binder mixture and aggregates does not degrade the properties of said road bitumen for road application, compared to an uncoated bitumen base.
  • the granules obtained by the process of the invention can be transported and / or stored and / or manipulated in the form of granules of solid material, in particular bitumen, solid at ambient temperature.
  • the solid material especially road bitumen, can be transported and / or stored at a high ambient temperature for a period greater than or equal to 2 months, preferably 3 months.
  • the high ambient temperature is from 20 ° C to 90 ° C, preferably from 20 ° C to 80 ° C, more preferably from 40 ° C to 80 ° C, still more preferably from 40 ° C to 60 ° C .
  • the granules of solid material, in particular bitumen, obtained by the process according to the invention have the advantage of keeping their divided form, and therefore of being able to be handled, after storage and / or transport at a temperature. high ambient. They have in particular the ability to flow under their own weight without flowing, which allows their storage in a packaging bags, drums or containers of all shapes and volumes and their transfer from this packaging to equipment, as a construction equipment (tank, mixer etc).
  • the granules of solid material, especially bitumen are preferably transported and / or stored in bulk in bags of 1 kg to 100 kg or 500 kg to 1000 kg commonly known in the field of road bitumens of "Big Bag ", said bags being preferably of heat-fusible material. They may also be transported and / or stored in bulk in cartons of 5 kg to 30 kg or in drums of 100 kg to 200 kg.
  • the invention also relates to a device for implementing the method described above.
  • This device described in FIGS. 1 to 3 is an apparatus for the extrusion in the form of pellets, also called “pastillation", on a tread, of a fluid mass of solid material at ambient temperature, which can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition, a clear binder.
  • a device is an improvement of the device described in US-4,279,579.
  • This device 1 comprises: a first cylindrical drum 4A disposed above the tread 6 and capable of rotation about a longitudinal axis, said first drum 4A comprising a plurality of first passages 5A through the periphery of the drum 4A, a second coaxial cylindrical drum 4B of the first drum 4A, comprising means 17 for admitting longitudinally into said second drum 4B the mass to be extruded and having on a part of its wall a plurality of second passages 5B directed towards the strip of bearing 6 and aligned radially with said first passages 5A, said wall portion 19 being disposed adjacent said first drum 4A, said first drum 4A being mounted for allow its continuous rotation 360 ° about the longitudinal axis relative to said second drum 4B so that the relative rotation between said drums 4A and 4B sequentially produces a misalignment and alignment of the first passages 5A and the second passages 5B for allowing the fluid mass to move radially outwardly through the aligned passages 5A, 5B and on the tread 6A, which
  • a reservoir 14 in which an additive composition 15 can be introduced the reservoir 14 being connected to the injection channel 3 through an injector 16 and allowing an injection of the additive composition 15 into the bitumen composition 2 at the channel 3, located downstream of the tank 11 and upstream of the double drum 4.
  • this device further comprises a spatula for removing excess mass from the perimeter of said first drum 4A, said spatula being directed towards said first drum 4A generally in the direction of rotation thereof, said spatula being firmly pressed against the perimeter of said first drum 4A in the region of said first passages 5A so as to scratch excess mass in said first passages 5A.
  • the first circumferentially-shifted first passages 4A are interconnected by grooves disposed along the periphery of the first drum 4A.
  • each groove preferably extends in a spiral direction, each groove connecting the openings in parallel planes which are arranged perpendicular to the axis of the drum and which are on different imaginary lines. longitudinally extending along the periphery of said first drum.
  • the invention further relates to a device for the extrusion of drops of a fluid mass on a tread 6, said device comprising: a first cylindrical drum 4A comprising a plurality of first passages 5A, a second cylindrical drum 4B disposed within said first drum 4A and comprising a plurality of second passages 5B, means 17 for admitting a fluid material into said second drum 4B, means for producing a relative rotation between said drums 4A, 4B, for periodically aligning said first passages 4A and second passages 4B, for depositing drops of fluid material through passages 4A, 4B, and on conveyor 6, said first and second drums 4A, 4B being mounted to separate radially from one another; the other during said relative rotation so as to form a gap between said first and second drums 4A, 4B under negative pressure at a location opposite the location where the passages are regularly aligned, so as to suck in the excess material mass in said passages 5A of said first drum 4A, this device further comprising, as illustrated in FIG.
  • a reservoir 14 in which an additive composition 15 can be introduced the reservoir 14 being connected to the injection channel 3 through an injector 16 and allowing an injection of the additive composition 15 into the bitumen composition 2 at the channel 3, located downstream of the tank 11 and upstream of the double drum 4.
  • said gap is formed by a recess in the periphery of the second drum 5B, the outer diameter of said recess being smaller than the inner diameter of said first drum 5A.
  • the device preferably comprises a spatula in contact with the periphery of the first drum to push the excess material into the first passages 5A, said spatula being disposed in the region of said gap.
  • the device preferably comprises a tight fitting around the periphery of the cover of the first drum 4B to cover the sector formed by the interstice.
  • the cover is preferably bordered at its longitudinal ends by curved guide ribs having a contour corresponding to that of the first drum.
  • the guide strips comprise front ends that are bevelled longitudinally inward to direct the excess material to the spatula.
  • the first drum 4A is rotatable.
  • the variation of the ball and ring softening temperature is measured according to the standard NF EN 1427 of said composition between the sample extracted from the upper part of the sample tube and the sample extracted from the lower part of the tube. 'sample.
  • the bitumen base B 2 is prepared from:
  • Bi 35/50 grade bitumen base, denoted by Bi, having a penetrability P 25 34 1/10 mm and a TBA of 52.6 ° C and commercially available from TOTAL group under the trademark AZALT ®;
  • the bitumen base B3 is prepared from:
  • Bi 35/50 grade bitumen base, denoted by Bi, having a penetrability P 25 34 1/10 mm and a TBA of 52.6 ° C and commercially available from TOTAL group under the trademark AZALT ®;
  • the bitumen is prepared in the following manner.
  • bitumen B 2 For the bitumen B 2 , the bitumen base Bi is introduced into a reactor maintained at 160 ° C. with stirring at 300 rpm for two hours. The additive Al is then introduced into the reactor. The contents of the reactor are maintained at 160 ° C. with stirring at 300 rpm for 1 hour.
  • bitumen base Bi is introduced into a reactor maintained at 160 ° C. with stirring at 300 rpm for two hours.
  • the additive Al and the additive A2 are then introduced into the reactor.
  • the contents of the reactor are maintained at 160 ° C. with stirring at 300 rpm for 1 hour.
  • the bituminous composition Bi, B 2 or B 3 is poured into the tank 11 of the device 1 and maintained at a temperature between 130 and 270 ° C.
  • a nozzle or a plurality of injection nozzles 3 makes it possible to transfer the bitumen composition Bi, B 2 or B 3 into the interior of the double pastillation drum 4 having a rotating outer drum, the two drums being equipped with slots , from nozzles and orifices for the pastillation of drops of bitumen 7 through the first fixed drum and orifices 5 having a diameter of between 2 and 10 mm from the rotating outer drum.
  • the drops 7 of diameter of between 2 and 10 mm are regularly pelletized through the orifices 5.
  • the drops of bitumen 7 are deposited on the upper face 6A of a tread 6, horizontal, driven by the rollers 12A and 12B, and one end of which is placed under the double drum 4.
  • the tread 6 with a length of 10 m and a width of 60 cm is equipped with four thermal conditioning device 8 respectively on two sections S1 and S2 comprising nozzles 8, 9 of water vaporization, on the lower face 6B of the tread 6.
  • the section SI conditions the tread 6 at ambient temperature (22-28 ° C.), and the section S2 cools the tread at a temperature below 20 ° C.
  • the drops of bitumen 7 are transferred to receiving means 10 consisting of a storage device being "big bags".
  • Granules of bitumen Gi, G 2 and G 3 were respectively obtained from the bituminous bases Bi, B 2 and B 3 and according to the method described above. These granules are solid at room temperature.
  • bitumen granules obtained above are left at room temperature for 10 to 15 minutes.
  • the granules thus formed are coated on their surface with an anti-caking compound and then sieved to remove excess anti-caking compound.
  • the granules of bitumen Gi ', G 2 ' and G3 ' are prepared from the granules of bitumen Gi, G 2 and G 3 obtained above and according to the method described above using as anti-caking compound fumed silica, available commercially under the reference AEROSIL ® 200.
  • the mass percentage of the coating for the granules Gi ', G 2 ' and G3 ' is about 1% by weight relative to the total mass of the bitumen of the granules.
  • This test is carried out in order to evaluate the resistance to the load of the bitumen granules prepared above at a temperature of 65 ° C. under a compressive force. Indeed, this test makes it possible to simulate the temperature and compression conditions of the granules on each other to which they are subjected during transport and / or storage in bulk in bags of 10 to 100 kg or in Big Bags of 500 to 1000 kg or in drums of 200 kg and to evaluate their resistance under these conditions.
  • the test of resistance to the load is carried out according to the following protocol: 5 mL of granules are placed in a syringe of 20 mL then the piston is placed on the granules as well as a mass of 208g, representing a force applied as in a Big Bag. The whole is placed in an oven at 65 ° C for at least 4 hours.
  • the observations are listed in Table 3 below.
  • the granules G 2 'and G 3 ' have a very good resistance at an ambient temperature of 60 ° C. insofar as they retain their initial shape and do not adhere not between them. Thus, the handling and transport / storage of said granules G 2 'and G 3 ' will be easy insofar as the granules do not melt and do not agglomerate with each other at high ambient temperature.

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Abstract

A method for manufacturing a material in divided form that is solid at ambient temperature and usable as a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for a bitumen/polymer composition, a clear binder, said method comprising the implementation of a device (1) intended for granulation that comprises at least two coaxial drums (4A, 4B) and a horizontal running belt (6): a fixed inner drum (4B) comprising at least one orifice (5B) and a rotating outer drum (4A) comprising a plurality of orifices (5A), said method comprising at least: (i) heating a first composition (2) to a temperature at which it is fluid, (ii) introducing the first composition (2) in the fluid state into the inner drum (4B) of the granulation device, (iii) distributing the first composition outwards in the form of drops (7) through the orifices (5A) in the rotating outer drum (4A), (iv) depositing the drops (7) on the running belt (6), and (v) optionally, coating the drops (7) with the second composition. A device for manufacturing these materials.

Description

PROCEDE DE FABRICATION DE MATERIAU SOUS FORME DE GRANULES UTILISABLE COMME LIANT ROUTIER OU LIANT  METHOD OF MANUFACTURING PELLET MATERIAL FOR USE AS A ROAD OR BINDER
D'ETANCHEITE ET DISPOSITIF POUR SA FABRICATION La présente invention concerne un procédé de fabrication d'un matériau sous forme divisée, solide à température ambiante, utilisable comme liant routier ou comme liant d'étanchéité, tel qu'un bitume routier, un brai, une solution mère pour composition bitume/polymère, un liant clair. Le matériau ainsi obtenu présente des propriétés avantageuses de résistance à la compression et au fluage lors de son transport et/ou de son stockage à température ambiante. Le procédé est économique et applicable à l'échelle industrielle. L'invention concerne également un dispositif pour la fabrication de ces matériaux.  The present invention relates to a method of manufacturing a material in divided form, solid at ambient temperature, which can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition, a clear binder. The material thus obtained has advantageous properties of resistance to compression and creep during its transport and / or storage at room temperature. The process is economical and applicable on an industrial scale. The invention also relates to a device for the manufacture of these materials.
Etat de la technique antérieure State of the art
De nombreux travaux ont porté sur la production de formes améliorées, des formes facilement manipulables, divisées, des matériaux utilisés pour la construction de chaussées afin de faciliter leur transport et leur mise en œuvre. Une autre contrainte lors de la formulation de ces matériaux est de maintenir leurs performances mécaniques, en particulier leur résistance aux fortes sollicitations routières, leur résistance au vieillissement.  Much work has focused on the production of improved forms, easily manipulated forms, divided, materials used for the construction of pavements to facilitate their transport and implementation. Another constraint in the formulation of these materials is to maintain their mechanical performance, in particular their resistance to heavy road stress, their resistance to aging.
La grande majorité du bitume est utilisée en construction, principalement pour la fabrication de chaussées routières ou dans l'industrie, par exemple pour des applications de toiture. Il se présente généralement sous la forme d'un matériau noir fortement visqueux, voire solide à température ambiante, qui se fluidifie en chauffant. The vast majority of bitumen is used in construction, mainly for the manufacture of road pavements or in industry, for example for roofing applications. It is generally in the form of a highly viscous black material, even solid at room temperature, which becomes fluid upon heating.
De manière générale, le bitume est stocké et transporté à chaud, en vrac, dans des camions-citernes ou par bateaux à des températures élevées de l'ordre de 120°C à 160°C. Or, le stockage et le transport du bitume à chaud présente certains inconvénients. D'une part, le transport du bitume à chaud sous forme liquide est considéré comme dangereux et il est très encadré d'un point de vue réglementaire. Ce mode de transport ne présente pas de difficultés particulières lorsque les équipements et les infrastructures de transport sont en bon état. Dans le cas contraire, il peut devenir problématique : si le camion-citerne n'est pas suffisamment calorifugé, la viscosité du bitume pourra augmenter durant un trajet trop long. Les distances de livraison du bitume sont donc limitées. D'autre part, le maintien du bitume à des températures élevées dans les cuves ou dans les camions-citernes consomme de l'énergie. En outre, le maintien du bitume à des températures élevées pendant une longue période peut affecter les propriétés du bitume et ainsi changer les performances finales de l'enrobé. In general, bitumen is stored and transported hot, in bulk, in tanker trucks or by boats at high temperatures in the range of 120 ° C to 160 ° C. However, the storage and transport of hot bitumen has certain disadvantages. On the one hand, the transport of hot bitumen in liquid form is considered dangerous and it is very framed from a regulatory point of view. This mode of transport presents no particular difficulties when the equipment and the transport infrastructures are in good condition. Otherwise, it can become problematic: if the tank truck is not sufficiently insulated, the viscosity of the bitumen may increase during a trip that is too long. Delivery distances for bitumen are therefore limited. On the other hand, the maintenance of bitumen at high temperatures in tanks or tank trucks consumes energy. In addition, maintaining the bitumen at elevated temperatures for a long time may affect the properties of the bitumen and thus change the final performance of the bitumen.
Pour pallier les problèmes du transport et du stockage du bitume à chaud, des conditionnements permettant le transport et le stockage des bitumes à température ambiante ont été développés. Ce mode de transport du bitume en conditionnement à température ambiante ne représente qu'une fraction minime des quantités transportées dans le monde, mais il correspond à des besoins bien réels pour les régions géographiques d'accès difficile et coûteux par les moyens de transport traditionnels.  To overcome the problems of transport and storage of hot bitumen, packaging for the transport and storage of bitumens at room temperature have been developed. This mode of transport of bitumen in room temperature packaging represents only a small fraction of the quantities transported in the world, but it corresponds to very real needs for geographical regions of difficult and expensive access by traditional means of transport.
A titre d'exemples de conditionnement, on peut citer les bitumes sous forme de granules transportés et/ou stockés dans des sacs, souvent utilisés dans des endroits où la température ambiante est élevée. Ces granules présentent l'avantage d'être facilement manipulables.  As examples of packaging, mention may be made of bitumen in the form of granules transported and / or stored in bags, often used in places where the ambient temperature is high. These granules have the advantage of being easily manipulated.
La même difficulté est rencontrée avec les brais et les compositions bitumineuses les comprenant, les liants clairs, les compositions bitume/polymère, notamment les solutions-mères de compositions bitume/polymère.  The same difficulty is encountered with pitches and bituminous compositions comprising them, clear binders, bitumen / polymer compositions, especially the stock solutions of bitumen / polymer compositions.
US 3 026 568 décrit un procédé de fabrication de granules de bitume recouverts d'un matériau poudreux, tel que de la poudre de calcaire. Le matériau bitumineux est extrudé au travers d'une buse dans une tour d'atomisation. Ce procédé peut uniquement être mis en œuvre avec des poudres minérales et dans des quantités non compatibles avec une production industrielle. Un autre inconvénient réside dans le fait que l'enrobage des granules peut être réalisé uniquement par poudrage.  US 3,026,568 discloses a method of manufacturing bitumen granules coated with a powdery material, such as limestone powder. The bituminous material is extruded through a nozzle into a spray tower. This process can only be carried out with mineral powders and in amounts not compatible with industrial production. Another disadvantage lies in the fact that the coating of the granules can be achieved solely by dusting.
La demande WO2009/153324 décrit des granules de bitume produits par co- extrusion d'une base bitume et d'une composition anti-agglomérante polymérique, en particulier du polyéthylène.  Application WO2009 / 153324 describes bitumen granules produced by coextrusion of a bitumen base and a polymeric anti-caking composition, in particular polyethylene.
La demande US 2011/0233105 décrit de l'asphalte solide à température ambiante sous forme de granules comprenant un cœur et une couche de revêtement, ces granules étant formés par extrusion au travers d'une filière.  The application US 2011/0233105 describes solid asphalt at ambient temperature in the form of granules comprising a core and a coating layer, these granules being formed by extrusion through a die.
L'inconvénient des procédés décrits ci-dessus est la mise en œuvre d'une étape d' extrusion qui est limitante du point de vue du rendement pour produire industriellement et à des coûts optimisés du bitume routier sous forme divisée et solide à température ambiante élevée. En outre, ce procédé est cher et ne permet que des cadences de production faibles. The disadvantage of the processes described above is the implementation of an extrusion step which is limiting in terms of efficiency to produce industrially and at optimized costs of divided and solid road bitumen. at high ambient temperature. In addition, this process is expensive and allows only low production rates.
Le document FR 2 998 896 décrit un procédé de production de granules de composition bitumineuse. Les granulés sont formés par découpe par cisaillement. Ce procédé présente l'inconvénient de ne pas pouvoir être appliqué dans des conditions économiquement satisfaisantes à des quantités élevées de matériaux.  The document FR 2 998 896 describes a process for producing granules of bituminous composition. The granules are formed by shear cutting. This method has the disadvantage that it can not be applied under economically satisfactory conditions to high quantities of materials.
On connaît par le document US 4 279 579 un dispositif d'extrusion permettant, à partir d'une masse fondue de matériau, de produire des granulés. Toutefois, ce document ne décrit pas d'utilisation spécifique de cet équipement pour la production de granules de matériaux utilisables comme liant routier ou comme liant d'étanchéité, tel qu'un bitume routier, un brai, une solution mère pour composition bitume/polymère, un liant clair. Lorsqu'un tel dispositif est utilisé avec une composition de ce type, il a été observé qu'en fonction des paramètres de structure et de fonctionnement de ce dispositif, on pouvait obtenir des granules ou une masse agglomérée de particules.  No. 4,279,579 discloses an extrusion device making it possible, from a melt of material, to produce granules. However, this document does not describe a specific use of this equipment for the production of granules of materials that can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition. , a clear binder. When such a device is used with a composition of this type, it has been observed that depending on the structure and operating parameters of this device, it was possible to obtain granules or an agglomerated mass of particles.
Le document US 2011/0185631 divulgue un dispositif et une méthode permettant la préparation de pastilles riches en asphaltènes par extrusion sous la forme de gouttes d'hydrocarbures lourds fondus puis par trempe des gouttes formées dans un milieu refroidissant.  The document US 2011/0185631 discloses a device and a method for the preparation of asphaltenes-rich pellets by extrusion in the form of melted heavy hydrocarbon drops and then by quenching the drops formed in a cooling medium.
Le document EP 0 511 197 divulgue un appareil permettant l'extrusion d'une masse fluide sur un support mobile. Cet appareil comprend notamment un premier cylindre fixe et un second cylindre disposé autour du premier cylindre et capable de tourner autour du premier cylindre, la masse fluide placée dans le premier cylindre est extrudée au travers de buses à la surface du second cylindre.  EP 0 511 197 discloses an apparatus for extruding a fluid mass on a mobile support. This apparatus comprises in particular a first fixed cylinder and a second cylinder arranged around the first cylinder and able to rotate around the first cylinder, the fluid mass placed in the first cylinder is extruded through nozzles on the surface of the second cylinder.
Le document WO 2016/110747 décrit un procédé de conditionnement de bitume sous la forme de pastilles caractérisé en ce que le bitume est chauffé puis écoulé au travers d'un cylindre rotatif perforé de façon à former des gouttelettes de bitume chaud qui sont ensuite refroidies sur une bande de roulement maintenue à une température de 8°C à 10°C.  The document WO 2016/110747 describes a process for packaging bitumen in the form of pellets, characterized in that the bitumen is heated and then passed through a rotary cylinder perforated so as to form droplets of hot bitumen which are then cooled on a tread maintained at a temperature of 8 ° C to 10 ° C.
Le document FR 2 765 229 divulgue des liants clairs et des liants bitumineux pouvant être mis sous la forme de pastilles ou de granulés.  Document FR 2 765 229 discloses clear binders and bituminous binders which can be in the form of pellets or granules.
La Demanderesse a donc cherché à mettre au point un procédé de fabrication de granules de matériaux utilisables comme liant routier ou comme liant d'étanchéité, tel qu'un bitume routier, un brai, une solution mère pour composition bitume/polymère, un liant clair, notamment de granules de bitume, capables d'être soumis à des températures ambiantes élevées sans fluer, en particulier des matériaux, notamment des bitumes, sous forme de granules dont l'adhésion et l'agglomération lors de leur transport et/ou stockage et/ou manipulation à température ambiante élevée est réduite par rapport aux granules de l'art antérieur. On a cherché à mettre au point un procédé extrapolable à des quantités élevées de matériau, qui soit économique, reproductible et qui puisse être mis en œuvre sans difficulté à une échelle industrielle. The Applicant has therefore sought to develop a process for producing granules of materials that can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition, a clear binder, in particular bitumen granules, capable of being subjected to high ambient temperatures without flowing, in particular materials, in particular bitumens, in the form of granules whose adhesion and agglomeration during their transport and / or storage and / or manipulation at high ambient temperature is reduced compared to the granules of the prior art. An attempt has been made to develop a process that can be extrapolated to high quantities of material, which is economical, reproducible and can be implemented without difficulty on an industrial scale.
Un objectif de la présente invention est de fournir un matériau utilisable comme liant routier ou comme liant d'étanchéité, tel qu'un bitume routier, un brai, une solution mère pour composition bitume/polymère, un liant clair, en particulier un bitume routier, transportable et/ou stockable et/ou manipulable à température ambiante élevée, et dont les propriétés sont conservées au cours du temps.  An object of the present invention is to provide a material that can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition, a clear binder, in particular a road bitumen. transportable and / or storable and / or manipulable at high ambient temperature, and whose properties are preserved over time.
En particulier, le but de la présente invention est de fournir un matériau utilisable comme liant routier ou comme liant d'étanchéité, tel qu'un bitume routier, un brai, une solution mère pour composition bitume/polymère, en particulier un bitume routier, transportable et/ou stockable pendant une durée supérieure à 2 mois, de préférence à 3 mois, et à température ambiante élevée, notamment à une température inférieure à 100°C, de préférence de 20°C à 80°C.  In particular, the object of the present invention is to provide a material that can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition, in particular a road bitumen, transportable and / or storable for a period greater than 2 months, preferably 3 months, and at high ambient temperature, especially at a temperature below 100 ° C, preferably from 20 ° C to 80 ° C.
Un autre objectif de l'invention est de proposer un matériau utilisable comme liant routier ou comme liant d'étanchéité, tel qu'un bitume routier, un brai, une solution mère pour composition bitume/polymère, un liant clair, en particulier un bitume routier, facilement manipulable, notamment à température ambiante élevée, en particulier à une température allant jusqu'à 100°C, de préférence de 20°C à 80°C.  Another object of the invention is to provide a material that can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition, a clear binder, in particular a bitumen. road, easily manipulated, especially at elevated ambient temperature, in particular at a temperature up to 100 ° C, preferably from 20 ° C to 80 ° C.
En particulier, le but de la présente invention est de fournir un matériau utilisable comme liant routier ou comme liant d'étanchéité, tel qu'un bitume routier, un brai, une solution mère pour composition bitume/polymère, un liant clair, en particulier un bitume routier, facilement manipulable après une durée de transport et/ou de stockage prolongée à température ambiante élevée, notamment pendant une durée de transport et/ou de stockage supérieure à 2 mois, de préférence supérieure à 3 mois, et à une température allant jusqu'à 100°C, de préférence entre 20°C et 80°C.  In particular, the object of the present invention is to provide a material which can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition, a clear binder, in particular a road bitumen, easily handled after a transport and / or prolonged storage time at high ambient temperature, in particular during a transport and / or storage time longer than 2 months, preferably longer than 3 months, and at a temperature ranging from up to 100 ° C, preferably between 20 ° C and 80 ° C.
Un objectif de la présente invention est de fournir un matériau utilisable comme liant routier ou comme liant d'étanchéité, tel qu'un bitume routier, un brai, une solution mère pour composition bitume/polymère, un liant clair, en particulier un bitume routier, sous une forme qui permette son écoulement sous forme solide à température ambiante, de façon à pouvoir le manipuler sans perte de matière. On a cherché à fournir un matériau utilisable comme liant routier ou comme liant d'étanchéité, tel qu'un bitume routier, un brai, une solution mère pour composition bitume/polymère, un liant clair, en particulier un bitume routier, qui soit sous une forme permettant de le conditionner dans un emballage, de le déconditionner, de le transvaser dans un équipement, même à une température ambiante élevée, sans avoir besoin de le chauffer, et sans perte de matière. Le matériau utilisable comme liant routier ou comme liant d'étanchéité, tel qu'un bitume routier, un brai, une solution mère pour composition bitume/polymère, en particulier le bitume proposé, est sous forme divisée et solide à température ambiante de telle sorte qu'il permet de résoudre de façon satisfaisante les problèmes évoqués ci-dessus. An object of the present invention is to provide a material which can be used as a road binder or as a sealing binder, such as a road bitumen, pitch, mother solution for bitumen / polymer composition, a clear binder, in particular a road bitumen, in a form that allows it to flow in solid form at room temperature, so that it can be handled without loss of material. It has been sought to provide a material which can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition, a clear binder, in particular a road bitumen, which is under a form that can be packaged in packaging, deconditioned, transferred to equipment, even at a high ambient temperature, without having to heat it, and without loss of material. The material that can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition, in particular the proposed bitumen, is in divided form and solid at ambient temperature in such a way that it solves satisfactorily the problems mentioned above.
Un autre objectif est de proposer un procédé industriel et économique pour fabriquer un matériau utilisable comme liant routier ou comme liant d'étanchéité, tel qu'un bitume routier, un brai, une solution mère pour composition bitume/polymère, un liant clair, en particulier du bitume routier, transportable et/ou stockable à température ambiante.  Another objective is to propose an industrial and economic process for producing a material that can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition, a clear binder, in particular road bitumen, transportable and / or storable at ambient temperature.
Un autre objectif de l'invention est de proposer un procédé industriel et économique pour fabriquer des enrobés à partir de bitume routier transportable et/ou stockable à température ambiante.  Another object of the invention is to provide an industrial and economical process for manufacturing asphalt from transportable road bitumen and / or storable at ambient temperature.
Un autre objectif de l'invention est de proposer un procédé écologique et économique pour transporter et/ou stocker et/ou manipuler un matériau utilisable comme liant routier ou comme liant d'étanchéité, tel qu'un bitume routier, un brai, une solution mère pour composition bitume/polymère, un liant clair, en particulier un bitume routier, à température ambiante, permettant d'éviter l'utilisation de moyens supplémentaires pour le maintien en température dudit matériau lors du transport et/ou du stockage et/ou de la manipulation et permettant de minimiser la présence de déchets et/ou de résidus.  Another objective of the invention is to propose an ecological and economical process for transporting and / or storing and / or handling a material that can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a solution mother for bitumen / polymer composition, a clear binder, in particular a road bitumen, at ambient temperature, making it possible to avoid the use of additional means for maintaining the temperature of said material during transport and / or storage and / or handling and to minimize the presence of waste and / or residues.
Résumé de l'invention Summary of the invention
L'invention concerne un procédé de fabrication de matériau utilisable comme liant routier ou comme liant d'étanchéité, solide à température ambiante sous forme de granules comprenant un cœur à base d'une première composition et optionnellement une couche de revêtement à base d'une seconde composition, la première composition comprenant au moins un matériau choisi parmi : une base bitume, un brai, un liant clair, ce procédé comprenant la mise en œuvre d'un dispositif destiné à la granulation qui comporte au moins deux tambours coaxiaux et une bande de roulement horizontale: un tambour intérieur fixe comportant au moins un orifice et un tambour extérieur rotatif comportant une pluralité d'orifices, les tambours étant placés au dessus d'une extrémité de la bande de roulement, horizontale, animée d'une vitesse VR, ce procédé comprenant au moins : The invention relates to a process for producing a material which can be used as a road binder or as a sealing binder, solid at room temperature in the form of granules comprising a core based on a first composition and optionally a coating layer based on a second composition, the first composition comprising at least one material chosen from: a bitumen base, a pitch, a clear binder, this process comprising the implementation of a device for granulation which comprises at least two coaxial drums and a horizontal tread: a fixed inner drum having at least one orifice and a rotating outer drum having a plurality of orifices, the drums being placed above an end of the tread, horizontal, driven by a speed V R , this method comprising at least:
(i) le chauffage de la première composition à une température à laquelle elle est fluide,  (i) heating the first composition to a temperature at which it is fluid,
(ii) l'introduction de la première composition à l'état fluide dans le tambour intérieur du dispositif de granulation,  (ii) introducing the first composition in the fluid state into the inner drum of the granulation device,
(iii) la distribution de la première composition vers l'extérieur, sous forme de gouttes au travers des orifices du tambour rotatif extérieur,  (iii) dispensing the first composition outward, in the form of drops through the orifices of the outer rotary drum,
(iv) le dépôt des gouttes sur la bande de roulement, et  (iv) the deposition of the drops on the tread, and
(v) optionnellement, l'enrobage des gouttes par la seconde composition.  (v) optionally, the coating of the drops by the second composition.
Selon un mode de réalisation préféré, le procédé comprend en outre, après l'étape (iv) entre les étapes (iv) et (v), une étape (iv') de refroidissement des gouttes de la première composition. According to a preferred embodiment, the method further comprises, after step (iv) between steps (iv) and (v), a step (iv ') for cooling the drops of the first composition.
Selon un mode de réalisation préféré, le refroidissement (iv') est réalisé au moyen d'un gradient de température sur la bande de roulement. According to a preferred embodiment, the cooling (iv ') is carried out by means of a temperature gradient on the tread.
Selon un mode de réalisation encore préféré, la bande de roulement est conditionnée à des températures différentes sur plusieurs sections (SI), ...(Si) de son parcours, avec i un entier allant de 2 à 8, de préférence de 2 à 4 par des moyens de conditionnement thermique. According to a still preferred embodiment, the tread is conditioned at different temperatures over several sections (SI), ... (Si) of its course, with i an integer ranging from 2 to 8, preferably from 2 to 4 by thermal conditioning means.
Selon un mode de réalisation préféré, la bande de roulement est conditionnée à température ambiante sur une première section (SI) de son parcours, et à une température inférieure ou égale à 20 °C, préférentiellement inférieure ou égale à 15 °C, sur une seconde section S2. According to a preferred embodiment, the tread is conditioned at ambient temperature on a first section (SI) of its course, and at a temperature less than or equal to 20 ° C, preferably less than or equal to 15 ° C, on a second section S2.
Selon un mode de réalisation encore préféré, le ratio de la longueur de la première section (SI) rapporté à la longueur de la seconde section (S2) va de 25/75 à 75/25. According to a still preferred embodiment, the ratio of the length of the first section (SI) to the length of the second section (S2) ranges from 25/75 to 75/25.
Selon un mode de réalisation préféré, le tambour extérieur rotatif du dispositif comporte des orifices de diamètre allant de 2 à 10 mm, de préférence de 2 à 8 mm, de préférence de 3 à 7 mm, encore mieux de 3,5 à 6 mm. According to a preferred embodiment, the rotary outer drum of the device comprises orifices having a diameter ranging from 2 to 10 mm, preferably from 2 to 8 mm, preferably from 3 to 7 mm, more preferably from 3.5 to 6 mm. .
Selon un mode de réalisation préféré, à l'étape (i) la première composition est portée à une température allant de 100 à 270°C, de préférence de 100 à 180 °C, de préférence de 120 à 160°C, encore mieux de 130 à 150 °C. According to a preferred embodiment, in step (i) the first composition is brought to a temperature ranging from 100 to 270 ° C, preferably from 100 to 180 ° C, preferably from 120 to 160 ° C, even better from 130 to 150 ° C.
Selon un mode de réalisation préféré, la vitesse VR de la bande de roulement est inférieure à 4 m/min. According to a preferred embodiment, the speed V R of the tread is less than 4 m / min.
Selon un mode de réalisation préféré, le procédé comprend en outre après l'étape (v) au moins une étape (vi) de séchage des granules enrobés, de préférence à une température allant de 20 à 60 °C, pendant une durée allant de 5 minutes à 5 heures, de préférence de 5 minutes à 2 heures. According to a preferred embodiment, the method further comprises, after step (v), at least one step (vi) of drying the coated granules, preferably at a temperature ranging from 20 to 60 ° C., for a duration ranging from 5 minutes to 5 hours, preferably 5 minutes to 2 hours.
Selon un mode de réalisation préféré, le matériau utilisable comme liant routier ou comme liant d'étanchéité est choisi parmi : une composition de bitume, un brai, un liant clair, une solution-mère bitume/polymère, une solution mère liant clair/polymère. According to a preferred embodiment, the material that can be used as a road binder or as a sealing binder is chosen from: a bitumen composition, a pitch, a clear binder, a bitumen / polymer stock solution, a clear binder / polymer stock solution .
Selon un mode de réalisation préféré, la première composition comprend au moins un matériau choisi parmi : une base bitume, un brai, un liant clair, une composition bitume/polymère, une composition liant clair/polymère, une solution- mère bitume/polymère ; une solution-mère liant clair/polymère ; un mélange de ces matériaux. Selon un mode de réalisation préféré, la seconde composition comprend au moins un composé anti-agglomérant. According to a preferred embodiment, the first composition comprises at least one material chosen from: a bitumen base, a pitch, a clear binder, a bitumen / polymer composition, a clear binder / polymer composition, a bitumen / polymer stock solution; a clear binder / polymer stock solution; a mixture of these materials. According to a preferred embodiment, the second composition comprises at least one anti-caking compound.
Selon un mode de réalisation préféré, le composé anti-agglomérant est choisi parmi : le talc ; les fines généralement de diamètre inférieur à 125 μιη, telles que les fines silicieuses, à l'exception des fines calcaires ; le sable tel que le sable de fontainebleau ; le ciment ; le carbone ; les résidus de bois tels que la lignine, le lignosulfonate, les poudres d'aiguilles de conifères, les poudres de cônes de conifères, notamment de pin ; les cendres de balles de riz ; la poudre de verre ; les argiles telles que le kaolin, la bentonite, la vermiculite ; l'alumine telle que les hydrates d'alumine ; la silice ; les dérivés de silice tels que les fumées de silice, les fumées de silice fonctionnalisées, notamment les fumées de silice hydrophobe ou hydrophile, les silices pyrogénées, notamment les silices pyrogénées hydrophobes ou hydrophiles, les silicates, les hydroxydes de silicium et les oxydes de silicium ; la poudre de matière plastique; la chaux ; le plâtre ; la poudrette de caoutchouc ; la poudre de polymères, tels que les copolymères styrène-butadiène (SB), les copolymères styrène-butadiène- styrène (SBS) et les mélanges de ces matériaux. According to a preferred embodiment, the anti-caking compound is chosen from: talc; fines generally of diameter less than 125 μιη, such as fine silicones, with the exception of fine limestones; sand such as fountain sand; cement ; carbon; wood residues such as lignin, lignosulphonate, conifer needle powders, conifer cone powders, especially pine powders; the ashes of rice balls; glass powder; clays such as kaolin, bentonite, vermiculite; alumina such as alumina hydrates; silica; silica derivatives such as silica fumes, functionalized silica fumes, in particular hydrophobic or hydrophilic silica fumes, pyrogenic silicas, especially hydrophobic or hydrophilic pyrogenic silicas, silicates, silicon hydroxides and silicon oxides ; plastic powder; lime; the plaster ; rubber crumb; polymer powder, such as styrene-butadiene copolymers (SB), styrene-butadiene-styrene copolymers (SBS) and mixtures of these materials.
Selon un mode de réalisation préféré, la seconde composition comprend au moins 10% en masse d'un ou plusieurs composés viscosifïants par rapport à la masse totale de la seconde composition. According to a preferred embodiment, the second composition comprises at least 10% by weight of one or more viscosifiers relative to the total mass of the second composition.
Selon un mode de réalisation préféré, le composé viscosifiant présente une viscosité dynamique supérieure ou égale à 50 mPa.s"1, de préférence de 50 mPa.s"1 à 550 mPa.s"1, plus préférentiellement de 80 mPa.s 1 à 450 mPa.s"1, la viscosité étant une viscosité Brookfield mesurée à 65°C. According to a preferred embodiment, the viscosifying compound has a dynamic viscosity greater than or equal to 50 mPa · s -1 , preferably from 50 mPa · s -1 to 550 mPa · s -1 , more preferably 80 mPa · s 1 at 450 mPa.s "1 , the viscosity being a Brookfield viscosity measured at 65 ° C.
Selon un mode de réalisation encore préféré, le composé viscosifiant est choisi parmi : According to a still preferred embodiment, the viscosifying compound is chosen from:
- les composés gélifiants, de préférence d'origine végétale ou animale, tels que la gélatine, l'agar-agar, les alginates, les dérivés de cellulose, les amidons, les amidons modifiés et les gommes gellanes ; les polyéthylène glycols (PEG) tels que les PEG ayant un poids moléculaire s entre 800 g.mol 1 et 8000 g.mol 1 ; gelling compounds, preferably of vegetable or animal origin, such as gelatin, agar-agar, alginates, cellulose derivatives, starches, modified starches and gellan gums; polyethylene glycols (PEG) such as PEGs having a molecular weight of between 800 gmol 1 and 8000 gmol 1 ;
les mélanges de tels composés. Selon un mode de réalisation préféré, la seconde composition comprend de 10 à mixtures of such compounds. According to a preferred embodiment, the second composition comprises from 10 to
90% en masse d'un ou plusieurs composés anti-agglomérants par rapport à la masse totale de la seconde composition, de préférence de 15 à 90 % en masse, et de 10 à 90% en masse d'au moins un composé viscosifïant par rapport à la masse totale de la seconde composition, de préférence de 10 à 85% en masse. 90% by weight of one or more anti-caking compounds relative to the total mass of the second composition, preferably from 15 to 90% by weight, and from 10 to 90% by weight of at least one viscosifying compound per relative to the total mass of the second composition, preferably from 10 to 85% by weight.
Selon un mode de réalisation préféré, la seconde composition est essentiellement constituée d'un ou plusieurs composés anti-agglomérants. According to a preferred embodiment, the second composition consists essentially of one or more anti-caking compounds.
Selon un mode de réalisation préféré, la base bitume présente une pénétrabilité à l'aiguille mesurée à 25°C selon la norme EN 1426 de 5 à 330 1/10 mm, de préférence de 20 à 220 1/10 mm. According to a preferred embodiment, the bitumen base has a needle penetration measured at 25 ° C according to the EN 1426 standard of 5 to 330 1/10 mm, preferably 20 to 220 1/10 mm.
Selon un mode de réalisation préféré, la première composition comprend en outre au moins un additif chimique choisi parmi : un composé organique, une paraffine, un acide polyphosphorique et leurs mélanges. According to a preferred embodiment, the first composition further comprises at least one chemical additive chosen from: an organic compound, a paraffin, a polyphosphoric acid and their mixtures.
Selon un mode de réalisation préféré, la première composition comprend : According to a preferred embodiment, the first composition comprises:
- de 30 à 40%) d'au moins un polymère,  from 30 to 40%) of at least one polymer,
- de 4 à 6% d'au moins un agent compatibilisant,  from 4 to 6% of at least one compatibilizing agent,
de 3% à 15% d'au moins un agent anti-agglomérant,  from 3% to 15% of at least one anti-caking agent,
les pourcentages étant en masse par rapport à la masse totale de la première composition. the percentages being in mass relative to the total mass of the first composition.
Selon un mode de réalisation préféré, la première composition présente une température de ramollissement bille et anneau (TBA) supérieure ou égale à 90°C, la TBA étant mesurée selon la norme EN 1427. Selon un mode de réalisation préféré, la première composition présente une pénétrabilité à l'aiguille mesurée à 25°C selon la norme EN 1426 de 5 à 45 l/10mm. According to a preferred embodiment, the first composition has a ball and ring softening temperature (TBA) greater than or equal to 90 ° C, the TBA being measured according to the EN 1427 standard. According to a preferred embodiment, the first composition has a needle penetration measured at 25 ° C according to the EN 1426 standard of 5 to 45 l / 10mm.
L'invention concerne également l'utilisation du procédé tel que décrit ci-dessus et ci-dessous de façon détaillée, pour fabriquer une composition de matériau utilisable comme liant routier ou comme liant de revêtement, solide à température ambiante, qui présente une stabilité au transport et au stockage à une température allant de 20 à 80°C pendant une durée supérieure ou égale à 2 mois, de préférence supérieure ou égale à 3 mois. The invention also relates to the use of the method as described above and below in detail, to produce a composition of material usable as a road binder or as a coating binder, solid at room temperature, which exhibits transport and storage at a temperature ranging from 20 to 80 ° C for a period greater than or equal to 2 months, preferably greater than or equal to 3 months.
L'invention concerne encore un dispositif utilisable pour la mise en œuvre d'un procédé tel que décrit ci-dessus et ci-dessous de façon détaillée, qui comprend au moins : un premier tambour cylindrique disposé au-dessus de la bande de roulement et capable d'une rotation autour d'un axe longitudinal, ledit premier tambour comprenant une pluralité de premiers passages à travers la périphérie du tambour, un second tambour cylindrique coaxial du premier tambour, comportant des moyens permettant d'admettre longitudinalement dans ledit second tambour la masse à extruder et comportant sur une partie de sa paroi une pluralité de seconds passages dirigés vers la bande de roulement et alignés radialement avec lesdits premiers passages, ladite partie de paroi étant disposée de façon adjacente audit premier tambour, ledit premier tambour étant monté pour permettre sa rotation continue sur 360 ° autour de l'axe longitudinal par rapport audit deuxième tambour de telle sorte que la rotation relative entre lesdits tambours produit de façon séquentielle un défaut d'alignement et un alignement des premiers passages et seconds passages pour permettre à la masse fluide de se déplacer radialement vers l'extérieur à travers les passages alignés, et sur la bande de roulement, ce dispositif comprenant en outre : The invention further relates to a device usable for carrying out a method as described above and below in detail, which comprises at least: a first cylindrical drum disposed above the tread and capable of rotation about a longitudinal axis, said first drum comprising a plurality of first passages through the periphery of the drum, a second coaxial cylindrical drum of the first drum, having means for longitudinally admitting in said second drum the mass to extrude and having on a portion of its wall a plurality of second passages directed towards the tread and radially aligned with said first passages, said wall portion being disposed adjacent to said first drum, said first drum being mounted to allow its rotation continues 360 ° about the longitudinal axis with respect to said second drum so that the relative rotation between said drums sequentially produces a misalignment and alignment of the first passages and second passages to allow the fluid mass to move radially outwardly through the aligned passages, and on the rolling, this device further comprising:
- un réservoir équipé de moyens de chauffage, et de moyens d'agitation,  a tank equipped with heating means, and stirring means,
- un canal, ou plusieurs canaux, d'injection permettant le transfert de la composition contenue dans le réservoir à l'intérieur du second tambour au travers des moyens d'admission,  a channel, or several channels, of injection allowing the transfer of the composition contained in the reservoir inside the second drum through the admission means,
ce dispositif étant caractérisé en ce qu'il comprend :  this device being characterized in that it comprises:
- un réservoir dans lequel on peut introduire une composition d'additifs, le réservoir étant relié au canal d'injection au travers d'un injecteur et permettant une injection de la composition d'additifs dans la composition de bitume au niveau du canal d'injection, situé en aval du réservoir et en amont du double tambour. a reservoir in which an additive composition can be introduced, the reservoir being connected to the injection channel through an injector and allowing a injecting the additive composition into the bitumen composition at the injection channel, located downstream of the reservoir and upstream of the double drum.
Figures figures
Figure 1 : représentation schématique d'un dispositif 1 selon l'invention  Figure 1: schematic representation of a device 1 according to the invention
Figure 2 : vue en coupe d'une partie du fonctionnement du double tambour 4 dans le dispositif 1 de l'invention  Figure 2: sectional view of a part of the operation of the double drum 4 in the device 1 of the invention
Figure 3 : représentation schématique en perspective des réservoirs et moyens d'injection de matériaux d'un dispositif 1 selon l'invention  FIG. 3: schematic representation in perspective of the reservoirs and material injection means of a device 1 according to the invention
Description détaillée detailed description
Les objectifs que la demanderesse s'est fixés ont été atteints grâce à la mise en forme des gouttes de compositions de matériau utilisable comme liant routier ou comme liant d'étanchéité, tel qu'un bitume routier, un brai, une solution mère pour composition bitume/polymère, un liant clair, en particulier de bitume, au moyen d'un dispositif de granulation particulier, ce dispositif permettant de former le coeur des structures cœur/enveloppe, dans des conditions qui sont reproductibles, extrapolables à grande échelle, économiques et fournissent des granules ayant des propriétés améliorées par rapport aux granules des mêmes matériaux connus de l'art antérieur.  The objectives that the applicant has set were achieved by shaping the drops of compositions of material that can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for composition bitumen / polymer, a clear binder, in particular bitumen, by means of a particular granulation device, this device making it possible to form the core of the core / shell structures, under conditions which are reproducible, extrapolatable on a large scale, economical and provide granules having improved properties with respect to the granules of the same materials known from the prior art.
L'expression « compris entre X et Y », inclut les bornes. Cette expression signifie donc que l'intervalle visé comprend les valeurs X, Y et toutes les valeurs allant de X à Y.  The expression "between X and Y" includes the terminals. This expression therefore means that the target range includes X, Y values and all values from X to Y.
Par « température ambiante », on entend la température résultante des conditions climatiques dans lesquelles est transporté et/ou stocké le matériau utilisable comme liant routier ou comme liant d'étanchéité, en particulier le bitume routier. Plus précisément, la température ambiante équivaut à la température atteinte lors du transport et/ou du stockage du matériau utilisable comme liant routier ou comme liant d'étanchéité, en particulier du bitume routier, étant entendu que la température ambiante implique qu'aucun apport de chaleur n'est apporté autre que celui résultant des conditions climatiques.  "Ambient temperature" means the temperature resulting from the climatic conditions in which the material used as a road binder or as a sealing binder, in particular road bitumen, is transported and / or stored. More specifically, the ambient temperature is equivalent to the temperature reached during transport and / or storage of the material that can be used as a road binder or as a sealing binder, in particular road bitumen, it being understood that ambient temperature implies that no heat is not brought other than that resulting from climatic conditions.
L'invention concerne des matériaux utilisables comme liant routier ou comme liant d'étanchéité, en particulier les bitumes susceptibles d'être soumis à une température ambiante élevée, en particulier une température allant jusqu'à 100°C, de préférence de 20°C à 80°C. The invention relates to materials which can be used as road binder or as sealing binder, in particular bitumens which may be subject to high ambient temperature, in particular a temperature of up to 100 ° C, preferably from 20 ° C to 80 ° C.
Par « matériau utilisable comme liant routier ou comme liant d'étanchéité » on entend au sens de la présente invention tout matériau susceptible d'être mis en œuvre pour cet usage, et notamment : les bases bitume, les compositions bitume/polymère, les compositions de bitume additivées, les brais, les solutions mères bitume-polymère, les liants clairs, les solutions mères liant clair-polymère, les mélanges de ces matériaux en toutes proportions.  By "material usable as a road binder or as a sealing binder" is meant in the sense of the present invention any material capable of being used for this purpose, and in particular: bitumen bases, bitumen / polymer compositions, compositions additivated bitumen, pitches, bitumen-polymer stock solutions, clear binders, light-polymer bonding stock solutions, mixtures of these materials in all proportions.
Par « matériau solide à température ambiante », on entend un matériau présentant un aspect solide à température ambiante quelles que soient les conditions de transport et/ou de stockage. Plus précisément, on entend par matériau solide à température ambiante, un matériau qui conserve son aspect solide tout au long du transport et/ou du stockage à température ambiante, c'est-à-dire un matériau qui ne flue pas à température ambiante sous son propre poids et de plus, qui ne flue pas lorsqu'il est soumis à des forces de pressions issues des conditions de transport et/ou de stockage.  By "solid material at room temperature" is meant a material having a solid appearance at ambient temperature whatever the transport and / or storage conditions. More specifically, solid material at ambient temperature is understood to mean a material which retains its solid appearance throughout transport and / or storage at ambient temperature, that is to say a material which does not flow at ambient temperature under its own weight and more, which does not flow when subjected to pressure forces from transport conditions and / or storage.
Par « bitume solide à température ambiante », on entend un bitume présentant un aspect solide à température ambiante quelles que soient les conditions de transport et/ou de stockage. Plus précisément, on entend par bitume solide à température ambiante, un bitume qui conserve son aspect solide tout au long du transport et/ou du stockage à température ambiante, c'est-à-dire un bitume qui ne flue pas à température ambiante sous son propre poids et de plus, qui ne flue pas lorsqu'il est soumis à des forces de pressions issues des conditions de transport et/ou de stockage.  By "solid bitumen at ambient temperature" is meant a bitumen having a solid appearance at ambient temperature regardless of the transport and / or storage conditions. More specifically, solid bitumen at ambient temperature is understood to mean a bitumen that retains its solid appearance throughout transport and / or storage at ambient temperature, that is to say a bitumen that does not flow at room temperature under its own weight and more, which does not flow when subjected to pressure forces from transport conditions and / or storage.
Par « couche de revêtement recouvrant tout en partie de la surface du cœur », on entend que la couche de revêtement recouvre au moins 90% de la surface du cœur, de préférence au moins 95% de la surface du cœur, plus préférentiellement au moins 99% de la surface du cœur.  "Coating layer covering all part of the surface of the core" means that the coating layer covers at least 90% of the surface of the core, preferably at least 95% of the surface of the core, more preferably at least 99% of the surface of the heart.
L'expression « consiste essentiellement en » suivie d'une ou plusieurs caractéristiques, signifie que peuvent être inclus dans le procédé ou le matériau de l'invention, outre les composants ou étapes explicitement énumérés, des composants ou des étapes qui ne modifient pas signifïcativement les propriétés et caractéristiques de l'invention. Le procédé selon l'invention permet d'obtenir des granules de matériau utilisable comme liant routier ou comme liant d'étanchéité, notamment de bitume, solide comprenant une couche de revêtement qui est résistante aux conditions climatiques et aux conditions de transport et/ou de stockage des liants routiers et/ou des liants d'étanchéité, en particulier qui est résistante aux conditions climatiques et aux conditions de transport et/ou de stockage du bitume routier solide, qui se casse facilement sous un effet de cisaillement mécanique, comme par exemple sous l'effet d'un cisaillement mécanique appliqué dans une cuve telle qu'un malaxeur ou un tambour-malaxeur lors de la fabrication d'enrobés. The expression "essentially consists of" followed by one or more characteristics, means that may be included in the method or material of the invention, in addition to the components or steps explicitly listed, components or steps that do not significantly modify the properties and characteristics of the invention. The method according to the invention makes it possible to obtain granules of material which can be used as road binder or as sealing binder, in particular solid bitumen, comprising a coating layer which is resistant to the climatic conditions and to the conditions of transport and / or storage of road binders and / or sealing binders, in particular which is resistant to climatic conditions and conditions of transport and / or storage of solid road asphalt, which breaks easily under a mechanical shear effect, such as for example under the effect of mechanical shear applied in a tank such as a kneader or kneading drum during the manufacture of asphalt.
Plus particulièrement, la couche de revêtement résiste au transport et/ou au stockage des liants routiers et/ou des liants d'étanchéité, en particulier du bitume, à température ambiante dans des « Big Bags » tout en étant cassante sous l'effet d'un cisaillement mécanique. Elle permet ainsi la libération du cœur en bitume lors de la fabrication d'enrobés.  More particularly, the coating layer is resistant to the transport and / or storage of road binders and / or sealing binders, in particular bitumen, at room temperature in "Big Bags" while being brittle under the effect of mechanical shearing. It thus allows the liberation of the bitumen core during the manufacture of asphalt.
Le procédé : The process
Le procédé de l'invention est mis en œuvre au moyen d'un dispositif qui est représenté sur les figures 1 à 3 et qui est illustré par la production d'une composition de bitume. Toutefois, le procédé pourrait être mis en œuvre, avec de simples adaptations des paramètres, à d'autres compositions telles que des brais, des liants clairs, des solutions-mères ou des mélanges de telles compositions en toutes proportions.  The method of the invention is implemented by means of a device which is shown in Figures 1 to 3 and which is illustrated by the production of a bitumen composition. However, the process could be implemented, with simple adjustments of the parameters, to other compositions such as pitches, clear binders, stock solutions or mixtures of such compositions in all proportions.
Une partie du dispositif tel que décrit sur la figure 1 est décrit de façon très détaillée dans le brevet US 4 279 579. Différents modèles de ce dispositif sont disponibles commercialement auprès de la société Sandvik sous le nom commercial de Rotoform. Ce dispositif 1 comprend un réservoir 11 équipé de moyens de chauffage (non représentés), et de moyens d'agitation 13, permettant de porter le contenant du réservoir 11, une composition de bitume 2, à l'état fluide. En fonction des additifs éventuellement présents dans la base bitume, la première composition 2 est portée à une température choisie pour éviter de dégrader lesdits additifs. Un canal ou plusieurs canaux d'injection 3 permet(tent) le transfert de la composition de bitume 2 fluide à l'intérieur du double tambour de pastillation 4. Comme cela est décrit dans le brevet US 4 279 579, l'injection de la composition de bitume 2 à l'intérieur du double tambour de pastillation 4 se fait, comme représenté sur la figure 3, au travers de moyens d'admission 17 placés à une extrémité latérale 18 du tambour 4. De façon innovante, le dispositif de l'invention comprend en outre un réservoir 14 dans lequel est placée une composition d'additifs 15. Ce réservoir 14 est relié au canal d'injection 3 au travers d'un injecteur 16 et permet une injection de la composition d'additifs 15 dans la composition de bitume 2 au niveau du canal 3, situé en aval du réservoir 11 et en amont du double tambour 4. En effet, certains additifs se dégradent lorsqu'ils sont stockés à chaud dans une composition de bitume et leur introduction dans le réservoir 11 entraînerait leur destruction avant que la composition de bitume 2 n'ait atteint le double tambour de pastillation 4. D'autres additifs décantent au stockage et conduisent à la formation d'une composition inhomogène. Aussi, la présence d'un réservoir d'additifs 14 équipé d'un injecteur 16 débouchant dans le canal d'injection 3 permet de surmonter ces difficultés et d'introduire dans le tambour de pastillage 4 une composition de bitume 2, de composition suffisamment stable dans le temps et suffisamment homogène pour former les granules de la composition souhaitée. Le tambour de pastillage 4 comprend un tambour interne fixe ou stator 4B équipé de moyens de chauffage (non représentés) permettant de maintenir la composition 2, éventuellement additivée, à l'état fluide. Il comporte un tambour externe rotatif 4A, les deux tambours étant équipés de fentes, de buses et d'orifices permettant la pastillation de gouttes de bitume 7 au travers du premier tambour fixe et des orifices 5 du tambour externe rotatif. Par exemple, comme représenté sur la figure 2, le premier tambour fixe 4B peut comprendre une fente longitudinale 5B et le second tambour rotatif 4A comporte des orifices 5A de taille sensiblement identique, alignés régulièrement, comme illustré dans le brevet US 4 279 579. D'autres arrangements des orifices des deux tambours sont possibles. Sous l'effet de la pression interne sensiblement homogène à l'intérieur du double tambour 4 du dispositif 1, lorsque les orifices 5B et 5A des deux tambours sont en regard l'un de l'autre, les gouttes 7 sont pastillées de façon régulière au travers desdits orifices 5 et présentent ainsi des tailles sensiblement homogènes. Les gouttes de bitume 7 sont déposées sur la face supérieure 6A d'une bande de roulement 6, horizontale, entraînée par les rouleaux 12A et 12B, et dont une extrémité est placée sous le double tambour 4. Les dimensions des orifices 5 du tambour externe rotatif permettent de contrôler la taille des gouttes de bitume 7. Par exemple les orifices 5A peuvent consister en des orifices sensiblement circulaires de diamètre 4 mm. La vitesse tangentielle VT du double tambour 4 est parallèle à la bande de roulement 6 et de même sens que la vitesse VR de la bande de roulement 6. La vitesse VR de la bande de roulement 6 est adaptée pour permettre un dépôt des gouttes 7 régulier et à distance suffisante les unes des autres pour éviter une agglomération ou une coalescence des gouttes 7. VR et VT sont sensiblement identiques. Par exemple, une vitesse VT = 3 m/minute donne des résultats satisfaisants. La bande de roulement 6 est équipée d'un premier dispositif de conditionnement thermique 8 sur une première section SI de sa longueur et d'un second dispositif de conditionnement thermique 9 sur une seconde section S2 de sa longueur. Le conditionnement permet le refroidissement progressif et la solidification des gouttes de bitume 7. Les moyens de conditionnement thermique peuvent consister en des buses 8, 9 de vaporisation d'un fluide, tel que de l'eau, sur la face inférieure 6B de la bande de roulement 6, à une température choisie. Par exemple, la section SI sur une longueur de 5 m conditionne la bande de roulement 6 à la température ambiante (22-28°C), et la section S2, sur une longueur de 5 m également, refroidit la bande de roulement à 20°C ou à 15°C. Selon une variante, la bande de roulement 6 peut être équipée d'un plus grand nombre (par exemple 3, 4, 5, 6) de dispositifs de conditionnement thermique successifs de façon à contrôler la température de la bande de roulement 6, section par section, de façon plus fine. La bande de roulement 6 peut présenter toutes dimensions adaptées afin de permettre le dépôt et le refroidissement progressif des gouttes de bitume 7. Par exemple, la bande de roulement 6 peut présenter une longueur de 10 m et une largeur de 60 cm. Les dimensions de la bande de roulement 6 sont adaptées notamment en fonction des dimensions du double tambour 4 (largeur du double tambour 4 notamment), des quantités de matière à traiter, du gradient de température souhaité. A l'extrémité de la bande de roulement opposée au double tambour 4, les gouttes de bitume 7 sont transférées vers des moyens de réception 10 qui peuvent consister par exemple en un dispositif de stockage, tel que des « big bags », un dispositif d'enrobage, ou une seconde bande de roulement permettant leur transfert vers un équipement de traitement tel qu'un équipement d'enrobage des gouttes de bitume 7. De préférence, les gouttes de bitume 7 sont transférées vers un dispositif d'enrobage (non représenté) tel qu'un dispositif d'enrobage par trempage, par pulvérisation ou tout autre dispositif adapté, en fonction de la composition d'enrobage choisie. Les gouttes de bitume 7 sont préparées à partir d'une première composition comprenant au moins un matériau choisi parmi : une base bitume, un brai, un liant clair, leurs mélanges. De préférence ladite première composition comprend au moins une ou plusieurs bases bitume. Le procédé de l'invention peut comprendre après l'étape de dépôt des gouttes 7 sur la bande de roulement 6 et avant une étape éventuelle d'enrobage, une étape (iv') de refroidissement des gouttes 7 de la première composition 2. Ce refroidissement peut être fait par tout moyen connu de l'homme du métier tel que stockage à une température basse, soufflage d'air froid, ... Le procédé de l'invention comprend en outre de façon optionnelle l'enrobage des gouttes par la seconde composition. Cet enrobage peut optionnellement être suivi d'un séchage des granules enrobés à une température allant de 20 à 60 °C, pendant une durée allant de 5 minutes à 5 heures, de préférence de 5 minutes à 2 heures. Part of the device as described in Figure 1 is described in great detail in US Patent 4,279,579. Various models of this device are commercially available from Sandvik under the trade name Rotoform. This device 1 comprises a reservoir 11 equipped with heating means (not shown), and stirring means 13, for carrying the container of the reservoir 11, a bitumen composition 2, in the fluid state. Depending on the additives possibly present in the bitumen base, the first composition 2 is brought to a temperature chosen to avoid degrading said additives. One or more injection channels 3 allow (the) transfer of the fluid bitumen composition 2 into the interior of the double pastillation drum 4. As described in US Pat. No. 4,279,579, the injection of bitumen composition 2 inside the double 4), as shown in FIG. 3, through intake means 17 placed at a lateral end 18 of the drum 4. In an innovative manner, the device of the invention further comprises a reservoir 14 in which is placed an additive composition 15. This reservoir 14 is connected to the injection channel 3 through an injector 16 and allows an injection of the additive composition 15 in the bitumen composition 2 at the channel 3, downstream of the tank 11 and upstream of the double drum 4. In fact, certain additives degrade when they are stored hot in a bitumen composition and their introduction into the tank 11 would lead to their destruction before the bitumen composition 2 has reached the double pastillation drum 4. Other additives decant on storage and lead to the formation of an inhomogeneous composition. Also, the presence of an additive reservoir 14 equipped with an injector 16 opening into the injection channel 3 makes it possible to overcome these difficulties and to introduce into the pelletizing drum 4 a composition of bitumen 2 of sufficiently sufficient composition stable over time and sufficiently homogeneous to form the granules of the desired composition. The pelletizing drum 4 comprises a fixed internal drum or stator 4B equipped with heating means (not shown) to maintain the composition 2, optionally additive, in the fluid state. It comprises a rotating outer drum 4A, the two drums being equipped with slots, nozzles and orifices allowing the pouring of bitumen drops 7 through the first fixed drum and the orifices 5 of the rotating outer drum. For example, as shown in FIG. 2, the first fixed drum 4B may comprise a longitudinal slot 5B and the second rotary drum 4A may have openings 5A of substantially identical size, regularly aligned, as illustrated in US Pat. No. 4,279,579. other arrangements of the orifices of the two drums are possible. Under the effect of the substantially homogeneous internal pressure inside the double drum 4 of the device 1, when the orifices 5B and 5A of the two drums are opposite one another, the drops 7 are regularly pelletized. through said orifices 5 and thus have substantially uniform sizes. The drops of bitumen 7 are deposited on the upper face 6A of a tread 6, horizontal, driven by the rollers 12A and 12B, and one end of which is placed under the double drum 4. The dimensions of the orifices 5 of the outer drum rotary control can control the size of the drops of bitumen 7. For example the orifices 5A may consist of substantially circular orifices of diameter 4 mm. The tangential velocity V T of the double drum 4 is parallel to the tread 6 and in the same direction as the speed V R of the tread 6. The speed V R of the tread 6 is adapted to allow a deposit of the drops 7 regular and sufficiently distant from each other to prevent agglomeration or coalescence drops 7. V R and V T are substantially identical. For example, a speed V T = 3 m / minute gives satisfactory results. The tread 6 is equipped with a first thermal conditioning device 8 on a first section S1 of its length and a second thermal conditioning device 9 on a second section S2 of its length. The packaging allows progressive cooling and solidification of the drops of bitumen 7. The thermal conditioning means may consist of nozzles 8, 9 for vaporizing a fluid, such as water, on the underside 6B of the strip 6, at a chosen temperature. For example, the SI section over a length of 5 m conditions the tread 6 at room temperature (22-28 ° C), and the section S2, along a length of 5 m also, cools the tread to 20 m. ° C or at 15 ° C. According to one variant, the tread 6 may be equipped with a larger number (for example 3, 4, 5, 6) of successive thermal conditioning devices so as to control the temperature of the tread 6, section by section, more finely. The tread 6 may have any suitable dimensions to allow the deposition and gradual cooling of the drops of bitumen 7. For example, the tread 6 may have a length of 10 m and a width of 60 cm. The dimensions of the tread 6 are adapted in particular according to the dimensions of the double drum 4 (width of the double drum 4 in particular), quantities of material to be treated, the desired temperature gradient. At the end of the tread opposite the double drum 4, the drops of bitumen 7 are transferred to receiving means 10 which may consist, for example, of a storage device, such as "big bags", coating, or a second tread allowing them to be transferred to treatment equipment such as bitumen drop coating equipment 7. Preferably, the drops of bitumen 7 are transferred to a coating device (not shown). ) such as a coating device by dipping, spraying or any other suitable device, depending on the chosen coating composition. The drops of bitumen 7 are prepared from a first composition comprising at least one material chosen from: a bitumen base, a pitch, a clear binder, and mixtures thereof. Preferably said first composition comprises at least one or more bitumen bases. The method of the invention may comprise, after the step of depositing drops 7 on the tread 6 and before a possible step of coating, a step (iv ') for cooling the drops 7 of the first composition 2. This cooling can be done by any means known to those skilled in the art such as storage at a low temperature, blowing cold air, ... The method of the invention further comprises optionally coating the drops by the second composition. This coating may optionally be followed by drying the coated granules at a temperature ranging from 20 to 60 ° C, for a period ranging from 5 minutes to 5 hours, preferably from 5 minutes to 2 hours.
De préférence, lors de la mise en œuvre du procédé de l'invention, le ratio en masse de la composition d'enrobage (seconde composition) par rapport à la masse de la première composition comprenant la base bitume, éventuellement additivée, formant le cœur est de 0,1 à 1, avantageusement de 0,2 à 0,9.  Preferably, during the implementation of the process of the invention, the mass ratio of the coating composition (second composition) relative to the mass of the first composition comprising the bitumen base, optionally additive, forming the core is from 0.1 to 1, preferably from 0.2 to 0.9.
Selon un premier mode de réalisation de l'invention, la composition d'enrobage, ou seconde composition, comprend un ou plusieurs composés anti-agglomérant.  According to a first embodiment of the invention, the coating composition, or second composition, comprises one or more anti-caking compounds.
Selon un second mode de réalisation de l'invention, la composition d'enrobage, ou seconde composition, comprend au moins un composé viscosifïant et au moins un composé anti-agglomérant.  According to a second embodiment of the invention, the coating composition, or second composition, comprises at least one viscosifying compound and at least one anti-caking compound.
Le composé viscosifïant et le composé anti-agglomérant sont tels que décrits ci- dessous.  The viscosifying compound and the anti-caking compound are as described below.
Ces différents enrobages peuvent être utilisés quelle que soit la nature chimique de la première composition, ils sont particulièrement adaptés aux compositions de bitume. Le cas échéant, l'homme du métier sait adapter la seconde composition d'enrobage en fonction de la nature de la première composition pour produire un résultat optimisé.  These different coatings can be used whatever the chemical nature of the first composition, they are particularly suitable for bitumen compositions. If need be, the person skilled in the art knows how to adapt the second coating composition according to the nature of the first composition to produce an optimized result.
Les granules : The granules:
Selon l'invention, le matériau utilisable comme liant routier ou comme liant d'étanchéité, notamment le bitume, solide à température ambiante est conditionné sous une forme divisée, c'est-à-dire sous forme d'unités de petite taille, que l'on nomme granules ou particules, comportant un cœur à base de bitume ou de brai ou de liant clair, ou d'un mélange des ces composants (première composition) et optionnellement une enveloppe ou coque ou enrobage ou couche de revêtement ou revêtement (seconde composition). According to the invention, the material that can be used as a road binder or as a sealing binder, especially bitumen, solid at room temperature is conditioned in a divided form, that is to say in the form of small units, which are called granules or particles, comprising a core based on bitumen or pitch or clear binder, or a mixture these components (first composition) and optionally an envelope or shell or coating or coating layer or coating (second composition).
De préférence, les granules de matériau utilisable comme liant routier ou comme liant d'étanchéité, notamment de bitume solide, selon l'invention peuvent avoir au sein d'une même population de granules, une ou plusieurs formes choisies parmi une forme cylindrique, sphérique ou ovoïde. La taille des granules est telle que la dimension moyenne la plus longue est de préférence de 2 à 10 mm, de préférence de 2 à 8 mm, de préférence de 3 à 7 mm, encore mieux de 3,5 à 6 mm. La taille des granules peut varier selon les dimensions des orifices du tambour rotatif employé. Généralement, tous les orifices du tambour rotatif sont de dimensions sensiblement identiques, toutefois, on peut prévoir de faire varier ces dimensions.  Preferably, the granules of material that can be used as road binder or as sealing binder, in particular solid bitumen, according to the invention can have, within the same population of granules, one or more forms chosen from a cylindrical, spherical form. or ovoid. The size of the granules is such that the longest average dimension is preferably 2 to 10 mm, preferably 2 to 8 mm, preferably 3 to 7 mm, more preferably 3.5 to 6 mm. The size of the granules may vary according to the dimensions of the orifices of the rotary drum employed. Generally, all the orifices of the rotary drum are of substantially identical dimensions, however, it is possible to vary these dimensions.
De préférence, les granules de matériau utilisable comme liant routier ou comme liant d'étanchéité, notamment de bitume, selon l'invention présentent un poids compris entre 0,1 g et 50 g, de préférence entre 0,2 g et 10 g, plus préférentiellement entre 0,2 g et 5 g. Première variante :  Preferably, the granules of material which can be used as road binder or as sealing binder, in particular bitumen, according to the invention have a weight of between 0.1 g and 50 g, preferably between 0.2 g and 10 g. more preferably between 0.2 g and 5 g. First variant:
Selon une première variante, les granules de matériau utilisable comme liant routier ou comme liant d'étanchéité, sont préparés à partir d'une première composition de bitume comprenant une ou plusieurs bases bitumes.  According to a first variant, the granules of material that can be used as a road binder or as a sealing binder are prepared from a first bitumen composition comprising one or more bitumen bases.
De préférence, les granules de bitume sont préparés à partir d'une première composition de bitume comprenant :  Preferably, the bitumen granules are prepared from a first bitumen composition comprising:
- une ou plusieurs bases bitumes,  one or more bitumen bases,
- de 0,1% à 5% en masse, de préférence de 0,5% à 4% en masse, plus préférentiellement de 0,5%> à 2,8% en masse, et encore plus préférentiellement de 0,5%) à 2,5%) en masse d'au moins un additif chimique,  from 0.1% to 5% by weight, preferably from 0.5% to 4% by weight, more preferably from 0.5% to 2.8% by weight, and even more preferably by 0.5%; ) at 2.5%) by mass of at least one chemical additive,
les pourcentages étant en masse par rapport à la masse totale de base bitume. the percentages being in mass relative to the total mass of bitumen base.
La base bitume et l'additif chimique sont tels que décrits ci-dessous. The bitumen base and the chemical additive are as described below.
De préférence, les granules de bitume sont préparés à partir d'une première composition de bitume comprenant : - une ou plusieurs bases bitumes, Preferably, the bitumen granules are prepared from a first bitumen composition comprising: one or more bitumen bases,
- de 0,1% à 5%> en masse, de préférence de 0,5%> à 4% en masse, plus préférentiellement de 0,5%> à 2,8% en masse, et encore plus préférentiellement de 0,5%) à 2,5%) en masse d'au moins un additif chimique et,  from 0.1% to 5% by weight, preferably from 0.5% to 4% by weight, more preferably from 0.5% to 2.8% by weight, and still more preferably from 0% to 5%) to 2.5%) by mass of at least one chemical additive and,
- de 0,5%o à 20%> en masse, de préférence de 2% à 20%> en masse, plus préférentiellement de 4% à 15% en masse d'au moins un agent anti-agglomérant, les pourcentages étant en masse par rapport à la masse totale de base bitume.  from 0.5% to 20% by weight, preferably from 2% to 20% by weight, more preferably from 4% to 15% by weight of at least one anti-caking agent, the percentages being mass relative to the total mass of bitumen base.
Selon un autre mode de réalisation préféré, les granules sont préparés à partir d'une première composition comprenant :  According to another preferred embodiment, the granules are prepared from a first composition comprising:
- une ou plusieurs bases bitume,  - one or more bitumen bases,
- entre 0,1 % et 5% en masse, de préférence entre 0,5% et 4% en masse, plus préférentiellement entre 0,5% et 2,8% en masse, et encore plus préférentiellement entre 0,5% et 2,5% en masse d'au moins un additif chimique,  between 0.1% and 5% by weight, preferably between 0.5% and 4% by weight, more preferably between 0.5% and 2.8% by weight, and even more preferentially between 0.5% and 2.5% by weight of at least one chemical additive,
- et entre 0,05% et 15% en masse, de préférence entre 0,1% et 10% en masse, plus préférentiellement entre 0,5% et 6% en masse d'au moins un adjuvant polymère oléfmique,  and between 0.05% and 15% by weight, preferably between 0.1% and 10% by weight, more preferably between 0.5% and 6% by weight of at least one olefinic polymer adjuvant,
les pourcentages étant en masse par rapport à la masse totale de base bitume. Selon un autre mode de réalisation préféré, les granules sont préparés à partir d'une première composition comprenant :  the percentages being in mass relative to the total mass of bitumen base. According to another preferred embodiment, the granules are prepared from a first composition comprising:
- une ou plusieurs bases bitume,  - one or more bitumen bases,
- de 30 à 40%) d'au moins un polymère,  from 30 to 40%) of at least one polymer,
- de 4 à 6% d'au moins un agent compatibilisant,  from 4 to 6% of at least one compatibilizing agent,
- de 3% à l5% d'au moins un agent anti-agglomérant,  from 3% to 15% of at least one anti-caking agent,
les pourcentages étant en masse par rapport à la masse totale de la première composition.  the percentages being in mass relative to the total mass of the first composition.
De façon optionnelle, les granules de bitume sont préparés à partir d'une première composition de bitume routier et recouvertes d'une seconde composition comprenant au moins un agent anti-agglomérant. Ce type de granules présente une structure cœur/enveloppe, également appelée cœur/couche de revêtement. Optionally, the bitumen granules are prepared from a first road bitumen composition and covered with a second composition comprising at least one anti-caking agent. This type of granules has a core / shell structure, also called core / coating layer.
Selon ce mode de réalisation, les granules comprennent, ou mieux sont essentiellement composés : - d'un cœur préparé à partir d'une première composition, According to this embodiment, the granules comprise, or better are essentially composed of: a heart prepared from a first composition,
- d'une couche de revêtement préparée à partir d'une seconde composition comprenant au moins un composé anti-agglomérant.  a coating layer prepared from a second composition comprising at least one anti-caking compound.
Les granules de bitume sont recouverts de Γ anti-agglomérant selon tout procédé connu, par exemple selon le procédé décrit dans le document US 3 026 568. The bitumen granules are covered with anti-caking agent according to any known method, for example according to the process described in US Pat. No. 3,026,568.
Selon un troisième mode de réalisation, les granules de bitume sont préparés à partir d'une première composition de bitume routier et recouvertes d'une seconde composition comprenant au moins un agent anti-agglomérant et au moins un agent viscosifïant. Selon ce mode de réalisation, les granules comprennent, ou mieux sont essentiellement composés de :  According to a third embodiment, the bitumen granules are prepared from a first road bitumen composition and covered with a second composition comprising at least one anti-caking agent and at least one viscosifying agent. According to this embodiment, the granules comprise, or better are essentially composed of:
- d'un cœur préparé à partir d'une première composition,  a heart prepared from a first composition,
- d'une couche de revêtement préparée à partir d'une seconde composition comprenant au moins un composé viscosifïant et au moins un composé anti- agglomérant.  a coating layer prepared from a second composition comprising at least one viscosifying compound and at least one anti-caking compound.
Les différentes couches d'enrobage peuvent être combinées avec toutes les variantes des premières compositions.  The different coating layers can be combined with all the variants of the first compositions.
Selon un mode de réalisation de l'invention, les granules de bitume solide peuvent comprendre en outre une ou plusieurs autres couches d'enrobage, à base d' anti-agglomérant recouvrant tout ou en partie la couche de revêtement du bitume solide selon l'invention.  According to one embodiment of the invention, the solid bitumen granules may further comprise one or more other coating layers, based on anti-caking agent covering all or part of the coating layer of the solid bitumen according to the invention. invention.
Avantageusement, les différents modes de réalisation décrits ci-dessus pour les granules peuvent se combiner entre eux. Seconde variante :  Advantageously, the various embodiments described above for the granules can be combined with one another. Second variant:
Selon une seconde variante, les granules de matériau utilisable comme liant routier ou comme liant d'étanchéité, sont préparés à partir d'une première composition comprenant au moins un brai.  According to a second variant, the granules of material that can be used as a road binder or as a sealing binder are prepared from a first composition comprising at least one pitch.
Selon un premier mode de réalisation, les granules sont constitués d'une première composition à base de brai.  According to a first embodiment, the granules consist of a first composition based on pitch.
Selon un second mode de réalisation, les granules sont constitués d'une première composition à base de brai et d'au moins une base bitume. Selon un premier mode de réalisation de cette seconde variante, la première composition comprend au moins un brai ayant une pénétrabilité à 25°C allant de 0 à 20 1/10 mm, une température de ramollissement bille et anneaux (TBA) allant de 115°C à 175°C, étant entendu que la pénétrabilité est mesurée selon la norme EN 1426 et que la TBA est mesurée selon la norme EN 1427. According to a second embodiment, the granules consist of a first composition based on pitch and at least one bitumen base. According to a first embodiment of this second variant, the first composition comprises at least one pitch having a penetrability at 25 ° C ranging from 0 to 20 1/10 mm, a ball and ring softening temperature (TBA) ranging from 115 ° C at 175 ° C., it being understood that the penetrability is measured according to the EN 1426 standard and that the TBA is measured according to the EN 1427 standard.
Selon un second mode de réalisation de cette seconde variante, la première composition comprend :  According to a second embodiment of this second variant, the first composition comprises:
- au moins un brai ayant une pénétrabilité à 25°C allant de 0 à 20 1/10 mm, une température de ramollissement bille et anneaux (TBA) allant de 115°C à 175°C, étant entendu que la pénétrabilité est mesurée selon la norme EN 1426 et que la TBA est mesurée selon la norme EN 1427,  at least one pitch having a penetrability at 25 ° C ranging from 0 to 20 1/10 mm, a ball and ring softening temperature (TBA) ranging from 115 ° C to 175 ° C, it being understood that the penetrability is measured according to EN 1426 and that the TBA is measured according to EN 1427,
- au moins une base bitume, et  at least one bitumen base, and
- au moins un additif chimique choisi parmi un composé organique, une paraffine, un acide polyphosphorique et leurs mélanges.  at least one chemical additive chosen from an organic compound, a paraffin, a polyphosphoric acid and their mixtures.
De préférence, selon ce second mode de réalisation, la première composition comprend :  Preferably, according to this second embodiment, the first composition comprises:
- au moins un brai ayant une pénétrabilité à 25°C allant de 0 à 20 1/10 mm, une température de ramollissement bille et anneaux (TBA) allant de 115°C à 175°C, étant entendu que la pénétrabilité est mesurée selon la norme EN 1426 et que la TBA est mesurée selon la norme EN 1427,  at least one pitch having a penetrability at 25 ° C ranging from 0 to 20 1/10 mm, a ball and ring softening temperature (TBA) ranging from 115 ° C to 175 ° C, it being understood that the penetrability is measured according to EN 1426 and that the TBA is measured according to EN 1427,
- au moins une base bitume, et  at least one bitumen base, and
- de 0,1% à 5% en masse, de préférence, de 0,5% à 4% en masse, plus préférentiellement de 0,5%> à 2,8% en masse, et encore plus préférentiellement de 0,5%) à 2,5%) en masse d'au moins un additif chimique choisi parmi un composé organique, une paraffine, un acide polyphosphorique et leurs mélanges,  from 0.1% to 5% by weight, preferably from 0.5% to 4% by weight, more preferably from 0.5% to 2.8% by weight, and even more preferably from 0.5% to %) at 2.5%) by mass of at least one chemical additive selected from an organic compound, a paraffin, a polyphosphoric acid and mixtures thereof,
les pourcentages étant en masse par rapport à la masse totale de la première composition.  the percentages being in mass relative to the total mass of the first composition.
Selon une première variante de ce second mode de réalisation, la première composition comprend :  According to a first variant of this second embodiment, the first composition comprises:
- au moins un brai ayant une pénétrabilité à 25°C allant de 0 à 20 1/10 mm, une température de ramollissement bille et anneaux (TBA) allant de 115°C à 175°C, étant entendu que la pénétrabilité est mesurée selon la norme EN 1426 et que la TBA est mesurée selon la norme EN 1427, - au moins une base bitume, at least one pitch having a penetrability at 25 ° C ranging from 0 to 20 1/10 mm, a ball and ring softening temperature (TBA) ranging from 115 ° C to 175 ° C, it being understood that the penetrability is measured according to EN 1426 and that the TBA is measured according to EN 1427, at least one bitumen base,
- de 0,1% à 5% en masse, de préférence, de 0,5% à 4% en masse, plus préférentiellement de 0,5%> à 2,8% en masse, et encore plus préférentiellement de 0,5%) à 2,5%) en masse d'au moins un additif chimique choisi parmi un composé organique, une paraffine, un acide polyphosphorique et leurs mélanges, et  from 0.1% to 5% by weight, preferably from 0.5% to 4% by weight, more preferably from 0.5% to 2.8% by weight, and even more preferably from 0.5% to %) at 2.5%) by mass of at least one chemical additive selected from an organic compound, a paraffin, a polyphosphoric acid and mixtures thereof, and
- de 0,5%o à 20%o en masse, de préférence, de 2% à 20%> en masse, plus préférentiellement de 4% à 15% en masse d'au moins un agent anti-agglomérant, les pourcentages étant en masse par rapport à la masse totale de la première composition.  from 0.5% to 20% by weight, preferably from 2% to 20% by weight, more preferably from 4% to 15% by weight of at least one anti-caking agent, the percentages being in mass relative to the total mass of the first composition.
Selon une seconde variante de ce second mode de réalisation, la première composition comprend :  According to a second variant of this second embodiment, the first composition comprises:
- au moins un brai ayant une pénétrabilité à 25°C allant de 0 à 20 1/10 mm, une température de ramollissement bille et anneaux (TBA) allant de 115°C à 175°C, étant entendu que la pénétrabilité est mesurée selon la norme EN 1426 et que la TBA est mesurée selon la norme EN 1427,  at least one pitch having a penetrability at 25 ° C ranging from 0 to 20 1/10 mm, a ball and ring softening temperature (TBA) ranging from 115 ° C to 175 ° C, it being understood that the penetrability is measured according to EN 1426 and that the TBA is measured according to EN 1427,
- au moins une base bitume,  at least one bitumen base,
- de 0,l%o à 5%o en masse, de préférence, de 0,5%> à 4% en masse, plus préférentiellement de 0,5% à 2,8% en masse, et encore plus préférentiellement de 0,5%o à 2,5%o en masse, voire de 0,5 à 2,8% en masse d'au moins un additif chimique choisi parmi un composé organique, une paraffine, un acide polyphosphorique et leurs mélanges, et  from 0.1% to 5% by weight, preferably from 0.5% to 4% by weight, more preferably from 0.5% to 2.8% by weight, and even more preferably from 0% to , 5% o to 2.5% by weight, or even 0.5 to 2.8% by weight of at least one chemical additive selected from an organic compound, a paraffin, a polyphosphoric acid and mixtures thereof, and
- de 0,05%o à 15% en masse, de préférence, de 0,1% à 10% en masse, plus préférentiellement de 0,5% à 6% en masse d'au moins un adjuvant polymère oléfmique,  from 0.05% to 15% by weight, preferably from 0.1% to 10% by weight, more preferably from 0.5% to 6% by weight of at least one olefinic polymer adjuvant,
les pourcentages étant en masse par rapport à la masse totale de la première composition.  the percentages being in mass relative to the total mass of the first composition.
Avantageusement l'invention concerne des granules de brai recouvertes sur au moins une partie de leur surface d'un anti-agglomérant tel que défini ci-dessous, de préférence sur l'ensemble de leur surface.  Advantageously, the invention relates to pitch granules coated on at least a portion of their surface with an anti-caking agent as defined below, preferably over their entire surface.
De préférence, la masse de Γ anti-agglomérant recouvrant au moins une partie de la surface des granules de brai est comprise entre 0,2% et 10% en masse, de préférence entre 0,5% et 8% en masse, plus préférentiellement entre 0,5% et 5% par rapport à la masse totale du brai. Preferably, the mass of anti-caking agent covering at least a portion of the surface of the pitch granules is between 0.2% and 10% by weight, preferably between 0.5% and 8% by weight, more preferably between 0.5% and 5% relative to the total mass of the pitch.
Avantageusement, la masse de l'anti-agglomérant recouvrant au moins une partie de la surface des granules de brai est d'environ 1% en masse par rapport à la masse totale du brai. Advantageously, the mass of the anti-caking agent covering at least a portion of the surface of the pitch granules is about 1% by weight relative to the total mass of the pitch.
De préférence, la couche d'anti-agglomérant recouvrant les granules de brai selon l'invention est continue de façon à ce qu'au moins 90%> de la surface desdites granules soit recouverte d'un anti-agglomérant, de préférence au moins 95%, plus préférentiellement au moins 99%. Preferably, the anti-caking layer covering the pitch granules according to the invention is continuous so that at least 90% of the surface of said granules is covered with an anti-caking agent, preferably at least 95%, more preferably at least 99%.
Troisième variante : Third variant:
Selon une troisième variante, les granules de matériau utilisable comme liant routier ou comme liant d'étanchéité, sont préparés à partir d'une première composition comprenant au moins un liant clair.  According to a third variant, the granules of material that can be used as road binder or as sealing binder are prepared from a first composition comprising at least one clear binder.
Les liants bitumineux classiques, en raison de la présence d'asphaltènes, sont de couleur noire et sont donc difficilement colorables. Les revêtements colorés sont de plus en plus utilisés car ils permettent entre autres, d'améliorer la sécurité des usagers de la route en identifiant clairement les voies spécifiques telles que les voies piétonnes, les pistes cyclables, les voies de bus. Ils permettent aussi de matérialiser certaines zones de danger comme les entrées d'agglomération ou les virages dangereux. Les revêtements colorés favorisent la visibilité en condition de faible luminosité, par exemple la nuit ou dans des sites particuliers tels que les tunnels. Enfin, ils permettent tout simplement d'améliorer l'aspect esthétique de la voirie urbaine et peuvent être utilisés pour les places publiques, les cours d'immeubles et d'écoles, les trottoirs, les rues piétonnes, les allées de jardins et de parcs, les aires de parking et de repos.  Conventional bituminous binders, due to the presence of asphaltenes, are black in color and are therefore difficult to color. Colored coatings are increasingly used because they allow, among other things, to improve the safety of road users by clearly identifying specific routes such as pedestrian routes, bike paths, bus lanes. They also make it possible to materialize certain danger zones such as entrances to agglomeration or dangerous turns. Colored coatings promote visibility in low light conditions, for example at night or in particular sites such as tunnels. Finally, they simply improve the aesthetic appearance of urban roads and can be used for public squares, courtyards and schools, sidewalks, pedestrian streets, garden and park paths. , parking and rest areas.
Par conséquent, pour toutes les applications précitées, on préfère utiliser des liants clairs de synthèse, ne contenant pas d'asphaltènes et pouvant être colorés.  Therefore, for all the above applications, it is preferred to use clear synthetic binders, not containing asphaltenes and can be colored.
Selon cette variante, la première composition comprend au moins un liant clair. Avantageusement, la première composition comprend au moins une base de liant clair et au moins un additif chimique choisi parmi un composé organique, une paraffine, un acide polyphosphorique et leurs mélanges. According to this variant, the first composition comprises at least one clear binder. Advantageously, the first composition comprises at least one clear binder base and at least one chemical additive chosen from an organic compound, a paraffin, a polyphosphoric acid and their mixtures.
Selon un mode de réalisation de l'invention, la première composition comprend de 0,1% à 5% en masse, de préférence de 0,5%> à 4% en masse, plus préférentiellement de 0,5%> à 2,8% en masse, et encore plus préférentiellement de 0,5% à 2,5% en masse dudit additif chimique par rapport à la masse totale dudit liant clair additivé.  According to one embodiment of the invention, the first composition comprises from 0.1% to 5% by weight, preferably from 0.5% to 4% by weight, more preferably from 0.5% to 2%, 8% by weight, and even more preferably from 0.5% to 2.5% by weight of said chemical additive relative to the total weight of said additivated clear binder.
Selon un mode de réalisation de l'invention, la première composition comprend - au moins une base de liant clair,  According to one embodiment of the invention, the first composition comprises - at least one clear binder base,
- entre 5% et 30% en masse, de préférence entre 6% et 28% en masse, plus préférentiellement entre 7% et 26% en masse du ou des additif(s) chimique(s) par rapport à la masse totale de ladite base de liant clair.  between 5% and 30% by weight, preferably between 6% and 28% by weight, more preferably between 7% and 26% by weight of the chemical additive (s) relative to the total mass of said clear binder base.
Dans ce cas la première composition est dite de liant clair concentré.  In this case the first composition is called clear concentrated binder.
Selon un mode de réalisation préféré, les granules sont préparés à partir d'une première composition comprenant : According to a preferred embodiment, the granules are prepared from a first composition comprising:
- une ou plusieurs bases de liant clair,  one or more clear binder bases,
- de 30 à 40%) d'au moins un polymère,  from 30 to 40%) of at least one polymer,
- de 4 à 6% d'au moins un agent compatibilisant,  from 4 to 6% of at least one compatibilizing agent,
- de 3% à l5% d'au moins un agent anti-agglomérant,  from 3% to 15% of at least one anti-caking agent,
les pourcentages étant en masse par rapport à la masse totale de la première composition.  the percentages being in mass relative to the total mass of the first composition.
On entend par liant clair solide à froid et sous forme divisée, un liant clair solide à température ambiante qui est conditionné sous une forme divisée, c'est-à-dire sous forme d'unités distinctes les unes des autres, que l'on nomme granules.  The term "cold solid binder" and "split form" means a clear solid binder at room temperature which is packaged in a divided form, that is to say in the form of units which are distinct from one another and which are name granules.
Le liant clair selon l'invention est désigné indifféremment dans la présente description « liant clair solide à froid et sous forme divisée » ou « liant clair additivé ». De préférence, le liant clair est une composition utilisable en substitution des liants à base de bitume pour la préparation par exemple d'enrobé bitumineux coloré. Un liant clair est exempt d'asphaltènes et peut donc garder la teinte naturelle du granulat auquel il est mélangé ou être aisément coloré à l'aide de pigments. The clear binder according to the invention is referred to indifferently in the present description "clear binder solid cold and divided form" or "clear binder additive". Preferably, the clear binder is a composition that can be used as a substitute for bitumen-based binders for the preparation, for example, of colored bituminous mix. A clear binder is free of asphaltenes and can therefore keep the natural color of the granulate to which it is mixed or be easily colored with pigments.
Comme pour les granules dont la première composition comprend une base bitume, les granules préparés à partir d'une première composition comprenant au moins un liant clair peuvent être enrobés d'une couche de revêtement préparée à partir :  As for the granules whose first composition comprises a bitumen base, the granules prepared from a first composition comprising at least one clear binder can be coated with a coating layer prepared from:
d'une seconde composition comprenant au moins un composé anti- agglomérant, ou  a second composition comprising at least one anti-caking compound, or
- d'une seconde composition comprenant au moins un composé viscosifiant et au moins un composé anti-agglomérant,  a second composition comprising at least one viscosifying compound and at least one anti-caking compound,
La base bitume The bitumen base
Avantageusement, le noyau ou cœur des granules de bitume solide selon l'invention est préparé à partir d'une première composition, qui est une composition de bitume routier, ladite première composition étant préparée en mettant en contact :  Advantageously, the core or core of the solid bitumen granules according to the invention is prepared from a first composition, which is a road bitumen composition, said first composition being prepared by bringing into contact:
- une ou plusieurs bases bitumes, et  one or more bitumen bases, and
éventuellement au moins un additif chimique.  optionally at least one chemical additive.
Au sens de l'invention, les termes « bitume » et « bitume routier » sont utilisés, de manière équivalente et indépendamment l'un de l'autre. Par « bitume » ou « bitume routier », on entend toutes compositions bitumineuses constituées d'une ou de plusieurs bases bitumes et comprenant éventuellement un ou plusieurs additifs chimiques, lesdites compositions étant destinées à une application routière.  For the purposes of the invention, the terms "bitumen" and "road bitumen" are used, in an equivalent manner and independently of one another. "Bitumen" or "road bitumen" means any bituminous compositions consisting of one or more bitumen bases and optionally comprising one or more chemical additives, said compositions being intended for road application.
Parmi les bases bitumes utilisables selon l'invention, on peut citer tout d'abord les bitumes d'origine naturelle, ceux contenus dans des gisements de bitume naturel, d'asphalte naturel ou les sables bitumineux et les bitumes provenant du raffinage du pétrole brut. Les bases bitumes selon l'invention sont avantageusement choisies parmi les bases bitumes provenant du raffinage du pétrole brut. Les bases bitumes peuvent être choisies parmi les bases bitumes ou mélanges de bases bitumes provenant du raffinage du pétrole brut, en particulier des bases bitumes contenant des asphaltènes ou des brais. Les bases bitumes peuvent être obtenues par des procédés conventionnels de fabrication des bases bitumes en raffinerie, en particulier par distillation directe et/ou distillation sous vide du pétrole. Ces bases bitumes peuvent être éventuellement viscoréduites et/ou désasphaltées et/ou rectifiées à l'air. Il est courant de procéder à la distillation sous vide des résidus atmosphériques provenant de la distillation atmosphérique de pétrole brut. Ce procédé de fabrication correspond, par conséquent, à la succession d'une distillation atmosphérique et d'une distillation sous vide, la charge alimentant la distillation sous vide correspondant aux résidus atmosphériques. Ces résidus sous vide issus de la tour de distillation sous vide peuvent être également utilisés comme bitumes. Il est également courant d'injecter de l'air dans une charge composée habituellement de distillais et de produits lourds provenant de la distillation sous vide de résidus atmosphériques provenant de la distillation du pétrole. Ce procédé permet d'obtenir une base soufflée, ou semi-soufflée ou oxydée ou rectifiée à l'air ou rectifiée partiellement à l'air. Among the bitumen bases that may be used according to the invention, mention may first 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. . The bitumen bases according to the invention are advantageously chosen from bitumen bases originating from the refining of crude oil. The bitumen bases may be chosen from bitumen bases or bitumen base mixtures derived from the refining of crude oil, in particular bitumen bases containing asphaltenes or pitches. The bitumen bases can be obtained by conventional processes for the manufacture of bitumen bases in a refinery, in particular by direct distillation and / or vacuum distillation of the oil. These bitumen bases may optionally be visbroken and / or deasphalted and / or rectified in air. It is vacuum distillation of atmospheric residues from atmospheric distillation of crude oil. This manufacturing process therefore corresponds to the succession of an atmospheric distillation and a distillation under vacuum, the feed supplying 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 charge usually composed of distillates and heavy products from the vacuum distillation of atmospheric residues from the distillation of petroleum. This method provides a base blown, or semi-blown or oxidized or rectified in air or rectified partially in air.
Les différentes bases bitumes obtenues par les procédés de raffinage peuvent être combinées entre elles pour obtenir le meilleur compromis technique. La base bitume peut aussi être une base bitume de recyclage. Les bases bitumes peuvent être des bases bitumes de grade dur ou de grade mou.  The various bitumen bases obtained by the refining processes can be combined with each other to obtain the best technical compromise. The bitumen base can also be a bitumen base for recycling. The bitumen bases may be bitumen bases of hard grade or soft grade.
Selon l'invention, pour les procédés conventionnels de fabrication des bases bitumes, on opère à des températures de fabrication comprises entre 100°C et 270°C, de préférence entre 100°C et 200°C, de préférence entre 140°C et 200°C, plus préférentiellement entre 140°C et 170°C, et sous agitation pendant une durée d'au moins 10 minutes, de préférence comprise entre 30 minutes et 10 heures, plus préférentiellement entre 1 heure et 6 heures. On entend par température de fabrication, la température de chauffage de la ou des bases bitumes avant mélange ainsi que la température de mélange. La température et la durée du chauffage varient selon la quantité de bitume utilisée et sont définies par la norme NF EN 12594.  According to the invention, for conventional methods of manufacturing bitumen bases, production temperatures of between 100 ° C. and 270 ° C., preferably between 100 ° C. and 200 ° C., preferably between 140 ° C. and 200 ° C, more preferably between 140 ° C and 170 ° C, and 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 term "manufacturing temperature" means the heating temperature of the bitumen base (s) before mixing as well as the mixing temperature. The temperature and the duration of the heating vary according to the quantity of bitumen used and are defined by the standard NF EN 12594.
Selon l'invention, les bitumes soufflés peuvent être fabriqués dans une unité de soufflage, en faisant passer un flux d'air et/ou d'oxygène à travers une base bitumineuse de départ. Cette opération peut être menée en présence d'un catalyseur d'oxydation, par exemple de l'acide phosphorique. Généralement, le soufflage est réalisé à des températures élevées, de l'ordre de 200 à 300°C, pendant des durées relativement longues typiquement comprises entre 30 minutes et 2 heures, en continu ou par lots. La durée et la température de soufflage sont ajustées en fonction des propriétés visées pour le bitume soufflé et en fonction de la qualité du bitume de départ. Préférentiellement, la base bitume mise en œuvre pour fabriquer les granules de l'invention présente une pénétrabilité à l'aiguille mesurée à 25°C selon la norme EN 1426 de 5 à 330 1/10 mm, de préférence de 20 à 220 1/10 mm. According to the invention, the blown bitumens can be manufactured in a blowing unit, by passing a stream of air and / or oxygen through a starting bituminous base. This operation can be carried out in the presence of an oxidation catalyst, for example phosphoric acid. Generally, the blowing is carried out at high temperatures, of 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 duration and the blowing temperature are adjusted according to the properties targeted for the blown bitumen and according to the quality of the starting bitumen. Preferably, the bitumen base used to manufacture the granules of the invention has a needle penetration measured at 25 ° C according to the EN 1426 standard of 5 to 330 1/10 mm, preferably 20 to 220 1 / 10 mm.
De manière bien connue, la mesure dite de « pénétrabilité à l'aiguille » est réalisée au moyen d'un test normalisé NF EN 1426 à 25°C (P25). Cette caractéristique de pénétrabilité est exprimée en dixièmes de millimètre (dmm ou 1/10 mm). La pénétrabilité à l'aiguille, mesurée à 25°C, selon le test normalisé NF EN 1426, représente la mesure de la pénétration dans un échantillon de bitume, au bout d'un temps de 5 secondes, d'une aiguille dont le poids avec son support est de 100 g. La norme NF EN 1426 remplace la norme homologuée NF T 66-004 de décembre 1986 avec effet au 20 décembre 1999 (décision du Directeur Général d'AFNOR en date du 20 novembre 1999).  In a well-known manner, the so-called "needle penetration" measurement is carried out by means of a standardized test NF EN 1426 at 25 ° C. (P25). This characteristic of penetrability is expressed in tenths of a millimeter (dmm or 1/10 mm). The needle penetration, 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. The NF EN 1426 standard replaces the homologated NF T 66-004 standard of December 1986 with effect from December 20, 1999 (decision of the Chief Executive Officer of AFNOR dated November 20, 1999).
La base de liant clair The clear binder base
On entend par base de liant clair, des compositions comprenant un agent plastifiant, par exemple une huile d'origine pétrolière ou d'origine végétale, un agent structurant, par exemple une résine hydrocarbonée, et un polymère. La composition des bases de liants clairs détermine certaines propriétés essentielles de ces liants, en particulier l'indice de plasticité, la viscosité du liant, ou la couleur qui doit être la plus claire possible.  By clear binder base is meant compositions comprising a plasticizer, for example an oil of petroleum or plant origin, a structuring agent, for example a hydrocarbon resin, and a polymer. The composition of the clear binder bases determines certain essential properties of these binders, in particular the plasticity index, the viscosity of the binder, or the color which must be as clear as possible.
Selon un mode de réalisation de l'invention, la base de liant clair comprend : According to one embodiment of the invention, the clear binder base comprises:
- un agent plastifiant, par exemple une huile naturelle ou synthétique, dépourvue d'asphaltènes, a plasticizing agent, for example a natural or synthetic oil, free of asphaltenes,
- un agent structurant, par exemple une résine hydrocarbonée ou végétale, - un copolymère,  a structuring agent, for example a hydrocarbon or vegetable resin, a copolymer,
- les cas échéant, des agents dopants, ou dopes, ou dopes d'adhésivité.  where appropriate, doping agents, or dopes, or dopants of adhesiveness.
Des compositions de liant clair sont décrites dans les demandes et brevets suivants et ces compositions de liant clair peuvent être mises en oeuvre comme base de liant clair dans la présente invention.  Clear binder compositions are described in the following applications and patents and these clear binder compositions can be used as a clear binder base in the present invention.
On peut utiliser comme base de liant clair un liant clair comprenant des huiles blanches hydrogénées comprenant au moins 60% de carbones paraffiniques (selon la méthode ASTM D2140), et une résine hydrocarbonée, le cas échéant en mélange avec des copolymères du type éthylène-acétate de vinyle (EVA) ou polyéthylène basse densité, par exemple du type EPDM (éthylène-propylène-diène-monomère), tel que décrit dans WO 01/53409. A clear binder comprising hydrogenated white oils comprising at least 60% paraffinic carbons (according to the ASTM D2140 method) and a hydrocarbon resin, optionally mixed with copolymers of the ethylene-vinyl acetate (EVA) or low-density polyethylene type, for example of the EPDM (ethylene-propylene-diene-monomer) type, as described in WO 01/53409.
On peut utiliser comme base de liant clair un liant clair comprenant une huile avec une teneur en naphténiques entre 35% et 80% et une résine hydrocarbonée, comme décrit dans EP 1783174. A clear binder comprising an oil with a naphthenic content between 35% and 80% and a hydrocarbon resin as described in EP 1783174 can be used as clear binder base.
On peut utiliser comme base de liant clair un liant clair comprenant une huile synthétique, une résine et un polymère de type SBS ou SIS, comme décrit dans EP 1473327. As a clear binder base a clear binder comprising a synthetic oil, a resin and an SBS or SIS type polymer can be used, as described in EP 1473327.
On peut utiliser comme base de liant clair un liant clair comprenant :  As a clear binder base a clear binder may be used comprising:
- au moins une huile d'origine pétrolière, de préférence une huile aromatique comprenant des extraits aromatiques de résidus de pétrole, obtenus par extraction ou désaromatisation de résidus de distillations de coupes pétrolières,  at least one oil of petroleum origin, preferably an aromatic oil comprising aromatic extracts of petroleum residues, obtained by extraction or dearomatization of residues of distillations of petroleum fractions,
- au moins une résine d'origine végétale, de préférence choisie parmi les esters de colophanes, les esters du glycérol et de colophanes, les esters du pentaérythritol et de colophanes, pris seuls ou en mélange, et  at least one resin of plant origin, preferably chosen from rosin esters, esters of glycerol and rosins, esters of pentaerythritol and rosins, taken alone or as a mixture, and
- au moins un latex, de préférence choisi parmi les latex de polymères acryliques, les latex de caoutchouc naturel, les latex de caoutchouc synthétiques, pris seuls ou en mélange, comme décrit dans WO 2009/150519.  at least one latex, preferably chosen from acrylic polymer latices, natural rubber latices and synthetic rubber latices, taken alone or as a mixture, as described in WO 2009/150519.
On peut utiliser comme base de liant clair un liant synthétique clair comprenant :As a clear binder base a clear synthetic binder can be used comprising:
- au moins une huile d'origine végétale de préférence choisie parmi les huiles de colza, de tournesol, de soja, de lin, d'olive, de palme, de ricin, de bois, de maïs, de courge, de pépins de raisin, de jojoba, de sésame, de noix, de noisette, d'amande, de karité, de macadamia, de coton, de luzerne, de seigle, de carthame, d'arachide, de coco et de coprah, et leurs mélanges, at least one oil of vegetable origin, preferably chosen from rapeseed, sunflower, soya, flax, olive, palm, castor oil, wood, corn, squash, grape seed oil , jojoba, sesame, walnut, hazelnut, almond, shea, macadamia, cotton, alfalfa, rye, safflower, peanut, coconut and copra, and mixtures thereof,
- au moins une résine d'origine pétrolière, de préférence choisie parmi les résines d'origine pétrolière hydrocarbonées issues de la copolymérisation de coupes pétrolières aromatiques, aliphatiques, cyclopentadiéniques prises seules ou en mélange et,  at least one resin of petroleum origin, preferably chosen from resins of petroleum hydrocarbon origin resulting from the copolymerization of aromatic, aliphatic, cyclopentadienic petroleum fractions taken alone or as a mixture and
- au moins un polymère, de préférence choisi parmi les copolymères de styrène et de butadiène, les copolymères de styrène et d'isoprène, les terpolymères éthylène/propène/diène, les polychloroprènes, les copolymères d'éthylène et d'acétate de vinyle, les copolymères d'éthylène et d'acrylate de méthyle, les copolymères d'éthylène et d'acrylate de butyle, les terpolymères éthylène/acrylate de méthyle/méthacrylate de glycidyle, les terpolymères éthylène/acrylate de butyle/anhydride maléique, les polypropylènes atactiques, pris seuls ou en mélanges, la quantité d'huile d'origine végétale dans le liant étant supérieure ou égale à 10% en masse et la quantité de polymère dans le liant étant inférieure ou égale à 15% en masse, comme décrit dans WO 2010/055491. Selon un autre mode de réalisation de l'invention, la base de liant clair comprend : at least one polymer, preferably chosen from copolymers of styrene and butadiene, copolymers of styrene and isoprene, terpolymers ethylene / propene / diene, polychloroprenes, copolymers of ethylene and vinyl acetate, copolymers of ethylene and methyl acrylate, copolymers of ethylene and butyl acrylate, ethylene / acrylate terpolymers of methyl / glycidyl methacrylate, ethylene / butyl acrylate / maleic anhydride terpolymers, atactic polypropylenes, taken alone or in mixtures, the amount of vegetable oil in the binder being greater than or equal to 10% by weight and the amount of polymer in the binder being less than or equal to 15% by weight, as described in WO 2010/055491. According to another embodiment of the invention, the clear binder base comprises:
(i) un agent plastifiant constitué d'une huile contenant une teneur totale en composés paraffîniques, mesurée selon la méthode ASTM D2140, d'au moins 50%>, de préférence d'au moins 60%> en poids, plus préférentiellement comprise entre 50%> et 90%, de préférence entre 60% et 80%, et  (i) a plasticizer consisting of an oil containing a total content of paraffinic compounds, measured according to ASTM D2140 method, of at least 50%, preferably at least 60% by weight, more preferably between 50%> and 90%, preferably between 60% and 80%, and
(ii) un copolymère à base de motifs diène conjugué et de motifs hydrocarbure monovinyl aromatique, par exemple à base de motif butadiène et de motifs styrène.  (ii) a copolymer based on conjugated diene units and aromatic monovinyl hydrocarbon units, for example based on a butadiene unit and on styrene units.
De préférence, l'huile est une huile synthétique issue des coupes d'unité de désasphaltage (ou « huile DAO »). Preferably, the oil is a synthetic oil derived from deasphalting unit cuts (or "DAO oil").
De préférence, l'huile contient une teneur totale en composés paraffîniques supérieure ou égale à 50%>, de préférence supérieure ou égale à 60%> en poids, et une teneur totale en composés naphténiques inférieure ou égale à 25% en poids, mesurée selon la méthode ASTM D2140.  Preferably, the oil contains a total content of paraffinic compounds greater than or equal to 50%, preferably greater than or equal to 60% by weight, and a total naphthenic compounds content of less than or equal to 25% by weight, measured. according to ASTM Method D2140.
De préférence, l'huile contient une teneur totale en composés paraffîniques supérieure ou égale à 50%>, de préférence supérieure ou égale à 60%> en poids, une teneur totale en composés naphténiques inférieure ou égale à 25% en poids, et une teneur totale en composés aromatiques inférieure ou égale à 25% en poids, mesurée selon la méthode ASTM D2140.  Preferably, the oil contains a total content of paraffinic compounds greater than or equal to 50%, preferably greater than or equal to 60% by weight, a total naphthenic compounds content of less than or equal to 25% by weight, and total content of aromatic compounds of less than or equal to 25% by weight, measured according to the ASTM D2140 method.
Par exemple, l'huile contient une teneur totale en composés paraffîniques, mesurée selon la méthode ASTM D2140, comprise entre 50% et 90%, de préférence entre 60% et 80% en poids, une teneur totale en composés naphténiques comprise entre 5% et 25% en poids, et une teneur totale en composés aromatiques comprise entre 5% et 25% en poids. For example, the oil contains a total content of paraffinic compounds, measured according to the ASTM D2140 method, of between 50% and 90%, preferably between 60% and 80% by weight, a total content of naphthenic compounds included between 5% and 25% by weight, and a total content of aromatic compounds of between 5% and 25% by weight.
De préférence, l'huile a un point d'aniline, mesuré selon la norme IS02977 : 1997, supérieur ou égal à 80°C, de préférence supérieur ou égal à 90 °C, par exemple supérieur à 100°C. Preferably, the oil has an aniline point, measured according to the standard IS02977: 1997, greater than or equal to 80 ° C, preferably greater than or equal to 90 ° C, for example greater than 100 ° C.
De préférence, la base de liant clair comprend de préférence (i) de 40 à 80% en poids d'agent plastifiant, (ii) de 20 à 50%> en poids de résine, (iii) de 1 à 7% en poids de copolymère ; et, (iv) éventuellement de 0,05%> à 0,5%> en poids de dope d'adhésivité, par exemple d'amine, par rapport au poids de base de liant clair. Avantageusement, la base de liant clair comprend de préférence (i) de 40 à 80% en poids d'agent plastifiant, (ii) de 20 à 50%> en poids de résine, (iii) de 1 à 7% en poids de copolymère ; et, (iv) de 0,05% à 0,5% en poids de dope d'adhésivité, par exemple d'amine, par rapport au poids de base de liant clair. Preferably, the clear binder base preferably comprises (i) from 40 to 80% by weight of plasticizer, (ii) from 20 to 50% by weight of resin, (iii) from 1 to 7% by weight copolymer; and, (iv) optionally from 0.05% to 0.5% by weight of tackifier, for example amine, based on the weight of clear binder. Advantageously, the clear binder base preferably comprises (i) from 40 to 80% by weight of plasticizer, (ii) from 20 to 50% by weight of resin, (iii) from 1 to 7% by weight of copolymer; and, (iv) from 0.05% to 0.5% by weight of tackifier, for example amine, based on the weight of clear binder base.
Avantageusement, la base de liant clair comprend également (i) de 45% à 70% en poids d'agent plastifiant, (ii) de 25 à 50% en poids de résine, (iii) de 1% à 7% en poids de copolymère ; et, (iv) éventuellement de 0,1% et 0,3% en poids de dope d'adhésivité, par rapport au poids total de base de liant clair. Advantageously, the clear binder base also comprises (i) from 45% to 70% by weight of plasticizer, (ii) from 25 to 50% by weight of resin, (iii) from 1% to 7% by weight of copolymer; and, (iv) optionally 0.1% and 0.3% by weight of tackifier, based on the total weight of clear binder base.
De préférence, la base de liant clair consiste essentiellement en (i) de 40 à 80% en poids d'agent plastifiant, (ii) de 20 à 50% en poids de résine, (iii) de 1 à 7% en poids de copolymère, par rapport au poids total de base de liant clair. Preferably, the clear binder base consists essentially of (i) from 40 to 80% by weight of plasticizer, (ii) from 20 to 50% by weight of resin, (iii) from 1 to 7% by weight of copolymer, based on the total weight of clear binder base.
Avantageusement, la base de liant clair consiste essentiellement en (i) de 40 à 80%) en poids d'agent plastifiant, (ii) de 20 à 50% en poids de résine, (iii) de 1 à 7% en poids de copolymère et (iv) de 0,05% à 0,5% en poids de dope d'adhésivité, par rapport au poids total de base de liant clair. Avantageusement, la base de liant clair consiste essentiellement également en (i) de 45%o à 70% en poids d'agent plastifiant, (ii) de 25 à 50% en poids de résine (iii) de 1%) à 7%) en poids de copolymère ; et, (iv) de 0,1% et 0,3% en poids de dope d'adhésivité, par rapport au poids total de base de liant clair. De préférence, le copolymère est un copolymère à base de motifs de styrène et de butadiène qui comprend une teneur pondérale en butadiène 1-2 allant de 5 à 70%. Advantageously, the clear binder base consists essentially of (i) from 40 to 80% by weight of plasticizer, (ii) from 20 to 50% by weight of resin, (iii) from 1 to 7% by weight of copolymer and (iv) from 0.05% to 0.5% by weight of tackifier, based on the total weight of clear binder base. Advantageously, the clear binder base essentially also consists of (i) from 45% to 70% by weight of plasticizer, (ii) from 25 to 50% by weight of resin (iii) of 1%) to 7% by weight of copolymer; and, (iv) 0.1% and 0.3% by weight of tackifier, based on the total weight of clear binder base. Preferably, the copolymer is a copolymer based on styrene and butadiene units which comprises a weight content of butadiene 1-2 ranging from 5 to 70%.
De préférence, le copolymère est avantageusement un copolymère à base de motifs de styrène et de butadiène qui comprend une teneur pondérale en butadiène 1-2 allant de 5 à 70% et une teneur pondérale en groupement 1,2-vinyle comprise entre 10 et 40%. Preferably, the copolymer is advantageously a copolymer based on styrene and butadiene units which comprises a weight content of butadiene 1-2 ranging from 5 to 70% and a weight content of 1,2-vinyl group of between 10 and 40. %.
Par exemple, ledit copolymère à base de motifs de styrène et de butadiène a une masse moléculaire moyenne en masse comprise entre 10 000 et 500 000, de préférence entre 50 000 et 200 000, et plus préférentiellement entre 50 000 et 150 000 daltons. De préférence, on utilisera un copolymère bloc styrène/butadiène ou bloc styrène/butadiène/ styrène . For example, said copolymer based on styrene and butadiene units has a weight average molecular weight of between 10,000 and 500,000, preferably between 50,000 and 200,000, and more preferably between 50,000 and 150,000 daltons. Preferably, a styrene / butadiene block copolymer or styrene / butadiene / styrene block copolymer will be used.
Les liants clairs selon l'invention sont avantageusement caractérisés en ce qu'ils présentent un indice de couleur inférieur ou égal à 4, de préférence inférieur ou égal à 3, tel que déterminé selon l'échelle ASTM DH4. En outre, ils peuvent avantageusement présenter une température de ramollissement Température Bille- Anneau déterminée selon la norme NF EN 1427 comprise entre 55°C et 90°C. The clear binders according to the invention are advantageously characterized in that they have a color index of less than or equal to 4, preferably less than or equal to 3, as determined according to the ASTM DH4 scale. In addition, they may advantageously have a Ball-Ring temperature softening temperature determined according to the NF EN 1427 standard of between 55 ° C. and 90 ° C.
De préférence, le liant clair utilisable selon l'invention a une pénétrabilité à 25°C, mesurée selon la norme NF EN 1426, comprise entre 10 et 220 1/10 mm, de préférence entre 30 et 100 1/10 mm, plus préférentiellement entre 40 et 80 1/10 mm. L'homme du métier peut moduler la pénétrabilité du liant clair utilisable dans l'invention notamment en choisissant judicieusement le rapport en poids [agent structurant/agent plastifiant] dans la composition de la base de liant clair. En effet, il est connu qu'une augmentation de ce rapport permet de diminuer la pénétrabilité à 25°C. Preferably, the clear binder used according to the invention has a penetrability at 25 ° C., measured according to standard NF EN 1426, of between 10 and 220 1/10 mm, preferably between 30 and 100 1/10 mm, more preferably between 40 and 80 1/10 mm. Those skilled in the art can modulate the penetrability of the clear binder used in the invention, in particular by judiciously choosing the weight ratio [structuring agent / plasticizer] in the composition of the clear binder base. Indeed, it is known that an increase in this ratio makes it possible to reduce the penetrability at 25 ° C.
Les bases de liants clairs mises en œuvre dans l'invention peuvent être préparées par exemple selon le procédé suivant comprenant les étapes de : (i) mélange de l'agent plastifiant, par exemple l'huile DAO, et chauffage à une température comprise entre 140-200°C, par exemple de 10 minutes à 30 minutes, The clear binder bases used in the invention may be prepared for example according to the following process comprising the steps of: (i) mixing the plasticizer, for example the oil DAO, and heating at a temperature between 140-200 ° C, for example from 10 minutes to 30 minutes,
(ii) ajout de l'agent structurant, par exemple la résine hydrocarbonée, mélange et chauffage à une température comprise entre 140-200°C, par exemple de 30 minutes à 2 heures,  (ii) adding the structuring agent, for example the hydrocarbon resin, mixing and heating at a temperature between 140-200 ° C, for example from 30 minutes to 2 hours,
(iii) ajout du ou des polymères, par exemple le SBS, mélange et chauffage à une température comprise entre 140-200°C, par exemple, de 90 minutes à 3 heures, de préférence de 90 minutes à 2 heures 30,  (iii) adding the polymer (s), for example SBS, mixing and heating at a temperature of between 140-200 ° C, for example 90 minutes to 3 hours, preferably 90 minutes to 2 hours 30 minutes,
(iv) ajout éventuel d'un dope d'adhésivité, mélange et chauffage à une température comprise entre 140-200°C, par exemple, de 5 minutes à 20 minutes.  (iv) optionally adding a dope of adhesiveness, mixing and heating at a temperature between 140-200 ° C, for example, from 5 minutes to 20 minutes.
L'ordre des étapes (i) à (iv) peut être modifié. The order of steps (i) to (iv) can be changed.
Selon un mode de réalisation de l'invention, les granules de liant clair comprennent en outre au moins un agent colorant tel que décrit ci-dessus, comme par exemple un pigment. According to one embodiment of the invention, the light binder granules further comprise at least one coloring agent as described above, such as for example a pigment.
Dans ces modes de réalisations, l'anti-agglomérant et/ou l'agent colorant sera choisi par l'homme du métier en fonction de la couleur du liant clair désiré. In these embodiments, the anti-caking agent and / or the coloring agent will be selected by those skilled in the art depending on the color of the desired clear binder.
Le brai Pitch
Selon le dictionnaire français, on entend par « brai », un résidu de distillation des goudrons de pétrole, de pétrole, de houille, de bois ou d'autres molécules organiques.  According to the French dictionary, "pitch" is a residue from the distillation of petroleum tars, oil, coal, wood or other organic molecules.
L'invention porte ici sur les résidus de distillation du pétrole, également appelés « brai de pétrole ». The invention relates here to the residues of petroleum distillation, also known as "petroleum pitch".
Au sens de l'invention, on utilisera indépendamment l'un de l'autre, les termes « brai », « brai de pétrole » et « brai de désasphaltage ». Les brais peuvent être obtenus par des procédés conventionnels de fabrication en raffinerie. Le procédé de fabrication correspond à la succession d'une distillation atmosphérique et d'une distillation sous vide. Dans un premier temps, le pétrole brut est soumis à une distillation à pression atmosphérique, qui conduit à l'obtention d'une phase gazeuse, de différents distillais et d'un résidu de distillât atmosphérique. Puis, le résidu de la distillation atmosphérique est soumis lui-même à une distillation sous pression réduite, appelée distillation sous vide, qui permet de séparer un gazole lourd, diverses coupes de distillais et un résidu de distillation sous vide. Ce résidu de distillation sous vide contient du « brai de pétrole » en concentration variable. For the purposes of the invention, the terms "pitch", "petroleum pitch" and "deasphalting pitch" will be used independently of one another. The pitches can be obtained by conventional refinery manufacturing processes. The manufacturing process corresponds to the succession of atmospheric distillation and vacuum distillation. In a first step, the crude oil is subjected to distillation at atmospheric pressure, which leads to the production of a gaseous phase, various distillates and an atmospheric distillate residue. Then, the residue of the atmospheric distillation is itself subjected to distillation under reduced pressure, called vacuum distillation, which makes it possible to separate a heavy gas oil, various sections of distillate and a distillation residue under vacuum. This vacuum distillation residue contains "petroleum pitch" in varying concentration.
Il est possible d'obtenir le « brai de pétrole » selon deux procédés : It is possible to obtain "oil pitch" by two methods:
lere procédé : l st method:
Le résidu de distillation sous vide est soumis à une opération de désalphatage par addition d'un solvant approprié, tel que le propane, qui permet ainsi de précipiter le brai et de le séparer des fractions légères telles que l'huile désaphaltée.  The vacuum distillation residue is subjected to a desalting operation by adding a suitable solvent, such as propane, which thus makes it possible to precipitate the pitch and to separate it from light fractions such as the unphased oil.
2nd procédé : 2 nd process:
Le résidu de distillation sous vide est soumis à une extraction au solvant, et plus précisément au furfural. Cet aldéhyde hétérocyclique présente la particularité de solubiliser sélectivement les composés aromatiques et poly cycliques. Ce procédé permet ainsi d'éliminer les extraits aromatiques et de récupérer le « brai de pétrole ».  The vacuum distillation residue is subjected to a solvent extraction, and more precisely to furfural. This heterocyclic aldehyde has the particularity of selectively solubilizing aromatic and polycyclic compounds. This process thus makes it possible to eliminate the aromatic extracts and to recover the "oil pitch".
Selon un mode de réalisation, le brai est un brai oxydé. According to one embodiment, the pitch is an oxidized pitch.
De préférence, le brai oxydé selon l'invention est obtenu par oxydation d'un mélange comprenant du brai et un diluant, tel qu'une essence légère, également appelé « fluxant » soumis à une opération d'oxydation dans une tour de soufflage en présence d'un catalyseur, à une température fixée et à une pression donnée. Preferably, the oxidized pitch according to the invention is obtained by oxidation of a mixture comprising pitch and a diluent, such as a light gasoline, also called "fluxing" subjected to an oxidation operation in a blowing tower. presence of a catalyst, at a fixed temperature and at a given pressure.
Par exemple, les brais oxydés peuvent être fabriqués dans une unité de soufflage, en faisant passer un flux d'air et/ou d'oxygène à travers un brai de départ. Cette opération peut être menée en présence d'un catalyseur d'oxydation, par exemple de l'acide phosphorique. Généralement, l'oxydation est réalisée à des températures élevées, de l'ordre de 200 à 300°C, pendant des durées relativement longues typiquement comprises entre 30 minutes et 2 heures, en continu ou par lots. La durée et la température d'oxydation sont ajustées en fonction des propriétés visées pour le brai oxydé et en fonction de la qualité du brai de départ. Les qualités mécaniques des brais sont généralement appréciées en déterminant une série de caractéristiques mécaniques par des essais normalisés, dont les plus utilisés sont la pénétrabilité à l'aiguille exprimée en 1/10 mm et le point de ramollissement déterminée par l'essai bille et anneau, encore appelée température de ramollissement bille et anneau (TBA). For example, oxidized pitches may be manufactured in a blowing unit, passing a stream of air and / or oxygen through a starting pitch. This operation can be carried out in the presence of an oxidation catalyst, for example phosphoric acid. Generally, the oxidation is carried out at high temperatures, of 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 duration and the oxidation temperature are adjusted according to the properties targeted for the oxidized pitch and according to the quality of the starting pitch. The mechanical properties of pitches are generally appreciated by determining a series of mechanical characteristics by standardized tests, the most used of which are needle penetration expressed in 1/10 mm and the softening point determined by the ball and ring test. , also called ball and ring softening temperature (TBA).
Selon un mode de réalisation de l'invention, le brai présente une pénétrabilité à l'aiguille à 25°C de 0 à 20 1/10 mm, de préférence de 0 à 15 1/10 mm, plus préférentiellement de 0 à 10 1/10 mm, étant entendu que la pénétrabilité est mesurée selon la norme EN 1426. According to one embodiment of the invention, the pitch exhibits needle penetration at 25 ° C. of 0 to 1/10 mm, preferably 0 to 1/10 mm, more preferably 0 to 10 1. / 10 mm, it being understood that the penetrability is measured according to standard EN 1426.
Selon un mode de réalisation de l'invention, le brai présente un point de ramollissement compris entre 115°C et 175°C. Parmi des exemples de brais utilisés dans l'invention, il y a des brais présentant respectivement un point de ramollissement compris entre 115°C et 125°C, entre 135 et 145°C ou encore entre 165 et 175°C. According to one embodiment of the invention, the pitch has a softening point of between 115 ° C and 175 ° C. Among examples of pitches used in the invention, there are pitches respectively having a softening point between 115 ° C and 125 ° C, between 135 and 145 ° C or between 165 and 175 ° C.
L 'agent plastifiant The plasticizer
Par « agent plastifiant », on entend au sens de l'invention, un constituant chimique permettant de fluidifier et de réduire la viscosité et le module du liant obtenu. Dans un mode de réalisation de l'invention, l'agent plastifiant est choisi parmi les huiles d'origine pétrolière, les huiles d'origine végétale et leur mélange. By "plasticizing agent" is meant in the sense of the invention, a chemical constituent for fluidizing and reducing the viscosity and the modulus of the binder obtained. In one embodiment of the invention, the plasticizing agent is chosen from oils of petroleum origin, oils of vegetable origin and their mixture.
Dans un mode de réalisation préféré de l'invention, les huiles d'origine végétale sont choisies parmi les huiles de colza, de tournesol, de soja, de lin, d'olive, de palme, de ricin, de bois, de maïs, de courge, de pépins de raisin, de jojoba, de sésame, de noix, de noisette, d'amande, de karité, de macadamia, de coton, de luzerne, de seigle, de carthame, d'arachide, de coco et de coprah, et leurs mélanges. De préférence, les huiles d'origine végétale sont choisies parmi les huiles de colza, de tournesol, de lin, de coco, de soja, et leurs mélanges. In a preferred embodiment of the invention, the oils of plant origin are chosen from rapeseed, sunflower, soybean, flax, olive, palm, castor oil, wood, corn, squash, grape seed, jojoba, sesame, walnut, hazelnut, almond, shea, macadamia, cotton, alfalfa, rye, safflower, peanut, coconut and copra, and their mixtures. Preferably, the oils of vegetable origin are chosen from rapeseed, sunflower, linseed, coconut and soybean oils, and mixtures thereof.
Dans un mode de réalisation préféré de l'invention, les huiles d'origine pétrolière sont choisies parmi les huiles aromatiques ou les huiles d'origine synthétique. In a preferred embodiment of the invention, the oils of petroleum origin are chosen from aromatic oils or oils of synthetic origin.
De préférence, les huiles aromatiques comprennent des extraits aromatiques de résidus de pétrole, obtenus par extraction ou désaromatisation de résidus de distillations de coupes pétrolières. Preferably, the aromatic oils comprise aromatic extracts of petroleum residues, obtained by extraction or dearomatization of residues of distillations of petroleum fractions.
Plus préférentiellement, les huiles aromatiques ont une teneur en composés aromatiques comprise entre 30 et 95% en poids, avantageusement comprise entre 50 et 90%) en poids, plus avantageusement comprise entre 60 et 85% en poids (méthode SARA : Saturés/Aromatiques/Résines/Asphaltènes). More preferably, the aromatic oils have an aromatic content of between 30 and 95% by weight, preferably between 50 and 90% by weight, more preferably between 60 and 85% by weight (SARA method: Saturated / Aromatic / resins / asphaltenes).
Plus préférentiellement, les huiles aromatiques ont une teneur en composés saturés comprise entre 1 et 20%> en poids, avantageusement comprise entre 3 et 15% en poids, plus avantageusement comprise entre 5 et 10%> en poids (méthode SARA : Saturés/ Aromatiques/Résines/ Asphaltènes). More preferably, the aromatic oils have a content of saturated compounds of between 1 and 20% by weight, advantageously between 3 and 15% by weight, more advantageously between 5 and 10% by weight (SARA method: Saturated / Aromatic / Resins / Asphaltenes).
Plus préférentiellement, les huiles aromatiques ont une teneur en composés résiniques comprise entre 1 et 10%> en poids, avantageusement comprise entre 3 et 5% en poids, (méthode SARA : Saturés/ Aromatiques/Résines/ Asphaltènes). Dans un mode préféré de réalisation de l'invention, les huiles d'origine synthétique sont issues des coupes de désasphaltage de distillation sous pression réduite (résidu sous vide, RSV) de pétrole brut (ci-après dénommée « huile DAO »). More preferably, the aromatic oils have a content of resin compounds of between 1 and 10% by weight, advantageously between 3 and 5% by weight, (SARA method: Saturated / Aromatic / Resins / Asphaltenes). In a preferred embodiment of the invention, the oils of synthetic origin come from distillation deasphalting cuts under reduced pressure (vacuum residue, RSV) of crude oil (hereinafter referred to as "DAO oil").
En particulier, dans un mode de réalisation préféré, l'agent plastifiant est constitué uniquement d'une huile DAO. Les teneurs en composés paraffmiques, naphténiques et aromatiques mentionnées dans la présente demande sont déterminées selon la norme ASTM D2140, en % poids par rapport au poids de l'huile. Dans un mode de réalisation spécifique, l'agent plastifiant est une huile, par exemple une huile DAO, contenant une teneur totale en composés paraffîniques d'au moins 50% en poids, de préférence d'au moins 60%> en poids, par exemple comprise entre 50%> et 90%>, de préférence entre 60%> et 90%>, plus préférentiellement entre 50%> et 80% et en particulier compris entre 55% et 70% ou en particulier compris entre 60% et 75%. In particular, in a preferred embodiment, the plasticizer consists solely of a DAO oil. The contents of paraffinic, naphthenic and aromatic compounds mentioned in the present application are determined according to the ASTM D2140 standard, in% by weight relative to the weight of the oil. In a specific embodiment, the plasticizer is an oil, for example a DAO oil, containing a total content of paraffinic compounds of at least 50% by weight, preferably at least 60% by weight, by weight. example between 50%> and 90%>, preferably between 60%> and 90%>, more preferably between 50%> and 80% and in particular between 55% and 70% or in particular between 60% and 75%. %.
Dans un mode de réalisation plus spécifique, l'agent plastifiant est une huile, par exemple une huile DAO, contenant en outre une teneur totale en composés naphténiques qui n'excède pas 25%, par exemple comprise entre 5% et 25%, et en particulier compris entre 10% et 25%. In a more specific embodiment, the plasticizer is an oil, for example a DAO oil, further containing a total naphthenic compounds content of not more than 25%, for example between 5% and 25%, and in particular between 10% and 25%.
Dans un mode de réalisation plus spécifique, l'agent plastifiant est une huile, par exemple une huile DAO, contenant en outre une teneur totale en aromatiques qui n'excède pas 25%, par exemple comprise entre 5% et 25%, et en particulier compris entre 8% et 18%. Dans un mode particulièrement préféré, l'agent plastifiant est une huile, par exemple une huile DAO, comprenant les teneurs respectives : In a more specific embodiment, the plasticizer is an oil, for example a DAO oil, further containing a total aromatic content of not more than 25%, for example between 5% and 25%, and between 8% and 18%. In a particularly preferred embodiment, the plasticizer is an oil, for example a DAO oil, comprising the respective contents:
(i) une teneur totale en composés paraffîniques compris entre 50% et(i) a total content of paraffinic compounds of between 50% and
90% ; 90%;
(ii) une teneur totale en composés naphténiques compris entre 5% et 25%, par exemple entre 15% et 25% ; et  (ii) a total content of naphthenic compounds of between 5% and 25%, for example between 15% and 25%; and
(iii) une teneur totale en composés aromatiques compris entre 5% et 25%, par exemple entre 10% et 15%.  (iii) a total content of aromatic compounds of between 5% and 25%, for example between 10% and 15%.
Dans un mode plus particulièrement préféré, l'agent plastifiant est une huile, par exemple une huile DAO, comprenant les teneurs respectives : (i) une teneur totale en composés paraffîniques compris entre 60% et 75% ;In a more particularly preferred embodiment, the plasticizer is an oil, for example a DAO oil, comprising the respective contents: (i) a total content of paraffinic compounds of between 60% and 75%;
(ii) une teneur totale en composés naphténiques compris entre 5% et 25%, par exemple entre 15% et 25% ; et (ii) a total content of naphthenic compounds of between 5% and 25%, for example between 15% and 25%; and
(iii) une teneur totale en composés aromatiques compris entre 5% et 25%, par exemple entre 10% et 15%. Des huiles répondant aux caractéristiques ci-dessus et utilisables pour la préparation du liant clair selon l'invention sont obtenues par les procédés de désasphaltage des résidus sous vide (RSV) issus du raffinage du pétrole, par exemple par un désasphaltage à l'aide d'un solvant en C3 à C6, de préférence au propane. Ces procédés de désasphaltages sont bien connus de l'homme du métier et sont décrits par exemple dans Lee et al 2014, Fuel Processing Technology 119 : 204-210 : Les résidus issus de la distillation sous vide (RSV) sont séparés selon leur poids moléculaire en présence de solvant C3 à C6 (par exemple le propane). L'huile dite DAO (« deasphalted oil ») ainsi obtenue est riche en paraffine, présente une très faible teneur en asphaltènes, a une température d'évaporation comprise entre 440°C et 750°C, et une gravité API bien supérieure à celle des résidus sous vide. (iii) a total content of aromatic compounds of between 5% and 25%, for example between 10% and 15%. Oils meeting the above characteristics and usable for the preparation of the clear binder according to the invention are obtained by vacuum residue deasphalting processes (RSV) from petroleum refining, for example by deasphalting with the aid of a C3 to C6 solvent, preferably propane. These deasphalting processes are well known to those skilled in the art and are described, for example, in Lee et al., 2014, Fuel Processing Technology 119: 204-210: The residues resulting from vacuum distillation (RSV) are separated according to their molecular weight. in the presence of C3 to C6 solvent (eg propane). The so-called DAO oil ("deasphalted oil") thus obtained is rich in paraffin, has a very low asphaltene content, has an evaporation temperature of between 440 ° C. and 750 ° C., and a API gravity much higher than that vacuum residues.
Les teneurs respectives en composés paraffïniques, naphténiques et aromatiques dépendent dans une certaine mesure de la nature du pétrole brut à l'origine de l'huile DAO et du processus de raffinage utilisé. L'homme du métier sait déterminer les teneurs respectives en composés paraffïniques, naphténiques et aromatiques d'une huile DAO par exemple à l'aide de la méthode de fractionnement SARA également décrite dans Lee et al 2014, Fuel Processing Technology 119 : 204-210 et ainsi sélectionner l'huile DAO approprié pour la préparation du liant clair selon l'invention. The respective contents of paraffinic, naphthenic and aromatic compounds depend to some extent on the nature of the crude oil at the origin of the DAO oil and the refining process used. Those skilled in the art can determine the respective contents of paraffinic, naphthenic and aromatic compounds of a DAO oil for example using the SARA fractionation method also described in Lee et al., 2014, Fuel Processing Technology 119: 204-210 and thus select the appropriate DAO oil for the preparation of the clear binder according to the invention.
Dans un mode de réalisation, la quantité d'agent plastifiant mise en œuvre dans le procédé de préparation de la base de liant clair est de 40% à 80%, de préférence de 45%o à 70%o en poids par rapport au poids total de base de liant clair. In one embodiment, the amount of plasticizer used in the process for preparing the clear binder base is 40% to 80%, preferably 45% to 70% by weight based on the weight total clear binder base.
L 'agent structurant The structuring agent
Par « agent structurant », on entend tout constituant chimique conférant des propriétés mécaniques et une cohésivité satisfaisante audit liant. By "structuring agent" is meant any chemical component imparting mechanical properties and satisfactory cohesiveness to said binder.
L'agent structurant utilisé dans le cadre de l'invention, est une résine, de préférence choisie parmi les résines d'origine pétrolière hydrocarbonée, par exemple issue de la copolymérisation de coupes pétrolières aromatiques, aliphatiques, cyclopentadiéniques, prises seules ou en mélange, de préférence issues de couples pétrolières aromatiques. Par exemple, il peut s'agir d'une résine thermoplastique polycycloaliphatique, par exemple du type homopolymères de cyclopentadiène hydrogénés, à faible masse moléculaire. The structuring agent used in the context of the invention is a resin, preferably chosen from resins of petroleum hydrocarbon origin, for example derived from the copolymerization of aromatic, aliphatic, cyclopentadienic petroleum fractions, taken alone or as a mixture, preferably from aromatic oil couples. For example, it may be a thermoplastic resin polycycloaliphatic, for example hydrogenated cyclopentadiene homopolymers, low molecular weight.
Plus particulièrement, la résine hydrocarbonée du type des cyclopentanes a un point de ramollissement (ou température Bille -Anneau, TBA, selon la norme NF T 66- 008) supérieur à 125°C, et un indice de couleur Gardner (selon la norme NF T 20- 030) égal au maximum à 1. More particularly, the hydrocarbon resin of the cyclopentane type has a softening point (or Ball-Ring temperature, TBA, according to standard NF T 66-008) greater than 125 ° C., and a Gardner color number (according to the NF standard). T 20-030) equal to at most 1.
D'autres exemples de résines utilisables comme agent structurant incluent, sans être limitatifs, les résines d'origine végétales obtenues à partir de végétaux et/ou de plantes. Elles peuvent être dites de récolte, c'est-à-dire récoltées à partir du végétal vivant. Elles peuvent être utilisées telles quelles, on parle alors de résines naturelles ou être transformées chimiquement, on parle alors de résines naturelles modifiées.  Other examples of resins that can be used as structuring agents include, but are not limited to, resins of vegetable origin obtained from plants and / or plants. They can be called harvest, that is to say harvested from the living plant. They can be used as they are, we speak then of natural resins or be transformed chemically, one speaks then of modified natural resins.
Parmi les résines de récolte, on trouve les résines accroïdes, le dammar, les colophanes naturelles, les colophanes modifiées, les esters de colophane et les résinâtes métalliques. Celles-ci peuvent être prises seules ou en mélange.  Among the harvest resins, there are the enhanced resins, dammar, natural rosins, modified rosins, rosin esters and metal resinates. These can be taken alone or mixed.
Parmi les colophanes naturelles, on peut citer les colophanes de gemme et de bois, en particulier de pin, et/ou de tall oil. Ces colophanes naturelles peuvent être prises seules ou en mélange.  Natural rosins include gem and wood rosin, especially pine, and / or tall oil. These natural rosins can be taken alone or as a mixture.
Parmi les colophanes modifiées, on peut citer les colophanes hydrogénées, les colophanes dismutées, les colophanes polymérisées et/ou les colophanes maléisées. Ces colophanes naturelles modifiées peuvent être prises seules ou en mélange, et subir un ou plusieurs traitements de dismutation, polymérisation et/ou maléisation.  Modified rosins include hydrogenated rosins, disproportionated rosins, polymerized rosins and / or maleic rosins. These modified natural rosins can be taken alone or as a mixture, and undergo one or more disproportionation, polymerization and / or maleization treatments.
Parmi les esters de colophanes, on peut citer les esters méthyliques de colophanes naturelles, les esters méthyliques de colophanes hydrogénées, les esters du glycérol et de colophanes naturelles, les esters du glycérol et de colophanes hydrogénées, les esters du glycérol et de colophanes dismutées, les esters du glycérol et de colophanes polymérisées, les esters du glycérol et de colophanes maléisées, les esters du pentaérythritol et de colophanes naturelles et les esters du pentaérythritol et de colophanes hydrogénées. Ces esters de colophanes peuvent être pris seuls ou en mélange et provenir de colophanes ayant subi un ou plusieurs traitement(s) de dismutation, polymérisation et/ou maléisation.  Among the rosin esters, mention may be made of the natural rosin methyl esters, the hydrogenated rosin methyl esters, the natural glycerol and rosin esters, the hydrogenated glycerol and rosin esters and the disubstituted glycerol and rosin esters, esters of glycerol and of polymerized rosins, esters of glycerol and of maleated rosin, esters of pentaerythritol and natural rosins and esters of pentaerythritol and hydrogenated rosins. These rosin esters can be taken alone or as a mixture and come from rosins having undergone one or more disproportionation, polymerization and / or maleization treatment (s).
Les esters du pentaérythritol et de colophanes naturelles et les esters du pentaérythritol et de colophanes hydrogénées sont les esters de colophanes préférés. Parmi les résinâtes métalliques, on peut citer les carboxylates métalliques, par exemple de Ca, Zn, Mg, Ba, Pb, Co, obtenus à partir de colophanes naturelles ou de colophanes modifiées. On préfère les résinâtes de calcium, les résinâtes de zinc, les résinâtes mixtes calcium/zinc, pris seuls ou en mélange. Esters of pentaerythritol and natural rosins and esters of pentaerythritol and hydrogenated rosins are the preferred rosin esters. Among the metal resinates, there may be mentioned metal carboxylates, for example of Ca, Zn, Mg, Ba, Pb, Co, obtained from natural rosins or modified rosins. Calcium resinates, zinc resinates, mixed calcium / zinc resinates, taken alone or as a mixture, are preferred.
Le rapport en poids entre l'agent structurant et l'agent plastifiant mis en œuvre pour la préparation du liant clair selon l'invention, est compris en général, de 0,3 à 1,5, par exemple de 0, 5 à 1.  The ratio by weight between the structuring agent and the plasticizer used for the preparation of the clear binder according to the invention is generally from 0.3 to 1.5, for example from 0.5 to 1 .
Dans un mode de réalisation spécifique, la quantité d'agent structurant mise en œuvre dans le procédé de préparation de la base de liant clair est de 25 à 50% en poids par rapport au poids total de base de liant clair. In a specific embodiment, the amount of structuring agent used in the process for preparing the clear binder base is 25 to 50% by weight relative to the total weight of clear binder base.
Le polymère The polymer
Le polymère mis en œuvre dans le procédé de préparation de la première composition est un copolymère à base de motifs diène conjugué et de motifs hydrocarbure monovinyl aromatique. Le diène conjugué est choisi de préférence parmi ceux comportant de 4 à 8 atomes de carbone par monomère, par exemple le butadiène, le 2-méthyl-l,3 -butadiène (isoprène), le 2,3-diméthyl-l,3-butadiène, le 1,3- pentadiène et le 1 ,2-hexadiène, chloroprène, butadiène carboxylé, isoprène carboxylé, en particulier le butadiène et l'isoprène, et leurs mélanges. L'hydrocarbure monovinyl aromatique est choisi de préférence parmi le styrène,The polymer used in the process for preparing the first composition is a copolymer based on conjugated diene units and monovinyl aromatic hydrocarbon units. The conjugated diene is preferably chosen from those comprising from 4 to 8 carbon atoms per monomer, for example butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3- butadiene, 1,3-pentadiene and 1,2-hexadiene, chloroprene, carboxylated butadiene, carboxylated isoprene, especially butadiene and isoprene, and mixtures thereof. The monovinyl aromatic hydrocarbon is preferably selected from styrene,
Γο-méthyl styrène, le p-méthyl styrène, le p-tert-butylstyrène, le 2,3 diméthyl- styrène, Pa- méthyl styrène, le vinyl naphtalène, le vinyl toluène, le vinyl xylène, et analogues ou leurs mélanges, en particulier le styrène. Α-methyl styrene, p-methyl styrene, p-tert-butyl styrene, 2,3-dimethyl styrene, p-methyl styrene, vinyl naphthalene, vinyl toluene, vinyl xylene, and the like or mixtures thereof, in especially styrene.
Plus particulièrement, le polymère consiste en un ou plusieurs copolymères choisis parmi les copolymères séquencés, de styrène et de butadiène, de styrène et d'isoprène, de styrène et de chloroprène, de styrène et de butadiène carboxylé ou encore de styrène et d'isoprène carboxylé. Un copolymère préféré est un copolymère à base de motifs butadiène et de motifs styrène tel que le copolymère bloc styrène/butadiène SB ou le copolymère bloc styrène/butadiène/styrène SB S. Le copolymère de styrène et de diène conjugué, en particulier le copolymère de styrène et de butadiène, possède avantageusement une teneur pondérale en styrène allant de 5 à 50%, de préférence de 20 à 50%>. More particularly, the polymer consists of one or more copolymers chosen from block copolymers of styrene and butadiene, styrene and isoprene, styrene and chloroprene, styrene and carboxylated butadiene or else styrene and isoprene. carboxyl. A preferred copolymer is a copolymer based on butadiene units and styrene units such as SB styrene / butadiene block copolymer or SB SB styrene / butadiene / styrene block copolymer. The styrene-conjugated diene copolymer, in particular the styrene-butadiene copolymer, advantageously has a weight content of styrene ranging from 5 to 50%, preferably from 20 to 50% by weight.
Le copolymère de styrène et de diène conjugué, en particulier le copolymère de styrène et de butadiène, possède avantageusement une teneur pondérale en butadiène (1-2 et 1-4) allant de 50 à 95%. Le copolymère de styrène et de diène conjugué, en particulier le copolymère de styrène et de butadiène, possède avantageusement une teneur pondérale en butadiène 1-2 allant de 5 à 70%, de préférence de 5 à 50%. Les motifs butadiène 1-2 sont les motifs qui résultent de la polymérisation via l'addition 1- 2 des motifs butadiène. The copolymer of styrene and conjugated diene, in particular the styrene-butadiene copolymer, advantageously has a weight content of butadiene (1-2 and 1-4) ranging from 50 to 95%. The copolymer of styrene and conjugated diene, in particular the styrene-butadiene copolymer, advantageously has a content by weight of butadiene 1-2 ranging from 5 to 70%, preferably from 5 to 50%. The 1,2-butadiene units are the units which result from the polymerization via the addition of 2-butadiene units.
La masse moléculaire moyenne en masse du copolymère de styrène et de diène conjugué, et notamment celle du copolymère de styrène et de butadiène, peut être comprise, par exemple, entre 10 000 et 500 000, de préférence entre 50 000 et 200 000 et plus préférentiellement de 50 000 à 150 000 daltons. Dans un mode de réalisation spécifique, la quantité totale de polymère mis en œuvre dans le procédé de l'invention est de 0,5 à 20% en masse, de préférence de 1 à 10%), de préférence de 1 à 7%, par exemple de 2% à 5% par rapport à la masse totale de base de base bitume, ou de liant clair. The weight average molecular weight of the copolymer of styrene and of conjugated diene, and in particular that of the styrene-butadiene copolymer, may be, for example, between 10,000 and 500,000, preferably between 50,000 and 200,000 and more. preferably from 50,000 to 150,000 daltons. In a specific embodiment, the total amount of polymer used in the process of the invention is 0.5 to 20% by weight, preferably 1 to 10%, preferably 1 to 7%, for example from 2% to 5% relative to the total weight of bitumen base base, or clear binder.
Dans un autre mode de réalisation spécifique, la quantité totale de polymère mis en œuvre dans le procédé de l'invention est de 20% à 50% en masse, par rapport à la masse totale de base bitume, ou par rapport à la masse totale de base de liant clair. In another specific embodiment, the total amount of polymer used in the process of the invention is 20% to 50% by weight, relative to the total weight of bitumen base, or in relation to the total mass. clear binder base.
Dans ce cas, la première composition est dite solution-mère de composition bitume/polymère ou solution-mère de composition liant clair/polymère. Elle est destinée à être transportée et stockée sous forme concentrée, puis diluée avec la quantité voulue de base bitume ou de base de liant clair juste avant son utilisation comme liant routier ou comme liant de revêtement. On peut, selon l'invention, former des granules de solution-mère de bitume ou de liant clair, de façon à faciliter leur transport et leur stockage à chaud ainsi que leur manipulation. Selon une variante de l'invention, le polymère est choisi parmi les polymères micronisés. De préférence, selon cette variante le polymère présente des particules de diamètre allant de 250 à 1000 μιη, de préférence de diamètre allant de 400 à 600 μιη. In this case, the first composition is said mother solution of bitumen / polymer composition or parent solution of clear binder / polymer composition. It is intended to be transported and stored in concentrated form, then diluted with the desired amount of bitumen base or clear binder base just prior to its use as a road binder or as a coating binder. According to the invention, it is possible to form granules of mother liquor of bitumen or clear binder, so as to facilitate their transport and their hot storage as well as their handling. According to a variant of the invention, the polymer is chosen from micronized polymers. Preferably, according to this variant, the polymer has particles of diameter ranging from 250 to 1000 μιη, preferably with a diameter ranging from 400 to 600 μιη.
Agent compatibilisant De préférence l'agent compatibilisant est choisi parmi les cires, par exemples les cires animales, les cires végétales, les cires minérales et leurs mélanges. Compatibilizing agent Preferably the compatibilizing agent is chosen from waxes, for example animal waxes, vegetable waxes, mineral waxes and their mixtures.
Les cires animales et végétales sont principalement composées de mélanges de dérivés d'acides gras (esters d'acides gras) tandis que les cires minérales sont des dérivés paraffmiques. Les dopes d'adhésivité Animal and vegetable waxes are mainly composed of mixtures of fatty acid derivatives (fatty acid esters) while mineral waxes are paraffinic derivatives. The adhesiveness dopes
Pour améliorer l'affinité réciproque entre le liant et les granulats et en assurer la pérennité, des dopes d'adhésivité peuvent également être utilisés dans la première composition, en mélange avec les autres composants, notamment le liant clair, ou la base bitume ou le brai. II s'agit par exemple de composés tensioactifs azotés dérivés des acides gras (aminés, polyamines, alkyl-polymanne etc ...). To improve the mutual affinity between the binder and the aggregates and to ensure their durability, adhesiveness dopes may also be used in the first composition, mixed with the other components, in particular the clear binder, or the bitumen base or the pitch. These are, for example, nitrogen-containing surfactant compounds derived from fatty acids (amines, polyamines, alkylpolymers, etc.).
Lorsqu'ils sont ajoutés à la première composition, les dopes d'adhésivité représentent en général entre 0,05% et 0,5%> en poids par rapport au poids de liant clair ou de base bitume ou de brai. Par exemple, dans un mode de réalisation spécifique, on ajoutera de 0,05%> à 0,5%> d'amine, de préférence de 0,1%> à 0,3%> d'amine par rapport à la masse totale de base de liant clair ou de base bitume ou de brai. When added to the first composition, the adhesiveness dopes generally represent between 0.05% and 0.5% by weight relative to the weight of light binder or bitumen base or pitch. For example, in a specific embodiment, from about 0.05% to about 0.5% amine, preferably from about 0.1% to about 0.3% amine, will be added to the mass. total base of clear binder or base bitumen or pitch.
Les agents colorants Coloring agents
Le liant synthétique clair peut également comprendre un ou plusieurs agents colorants, tels que des pigments minéraux ou des colorants organiques. Les pigments sont sélectionnés suivant la teinte, la couleur souhaitée pour le revêtement. On utilisera par exemple des oxydes métalliques tels que des oxydes de fer, des oxydes de chrome, des oxydes de cobalt, des oxydes de titane pour obtenir les couleurs rouge, jaune, gris, vert bleu ou blanc. Les pigments peuvent être ajoutés, indifféremment dans le liant clair ou dans l'enrobé (en mélange avec les granulats par exemple) ou dans une émulsion du liant clair. The clear synthetic binder may also include one or more coloring agents, such as inorganic pigments or organic dyes. The pigments are selected according to the color, the desired color for the coating. For example, metal oxides such as iron oxides, chromium oxides, cobalt oxides, titanium oxides will be used to obtain the colors red, yellow, gray, blue green or white. Pigments can be added, indifferently in the clear binder or in the mix (mixed with the aggregates for example) or in an emulsion of the clear binder.
L 'additif chimique The chemical additive
La base bitume ou le liant clair ou le mélange de base bitume et de brai peut en outre comprendre au moins un additif chimique choisi parmi : un composé organique, une paraffine, un acide polyphosphorique et leurs mélanges.  The bitumen base or the light binder or the mixture of base bitumen and pitch may further comprise at least one chemical additive selected from: an organic compound, a paraffin, a polyphosphoric acid and mixtures thereof.
En particulier, lorsque le matériau solide comprend au moins un additif chimique, celui-ci est en quantité adaptée pour que sa pénétrabilité soit de préférence de 5 à 50 l/10mm et/ou que la température de ramollissement bille et anneau (TBA) soit, de préférence, supérieure ou égale à 60°C, étant entendu que la pénétrabilité est mesurée à 25°C selon la norme EN 1426 et la TBA selon la norme EN 1427.  In particular, when the solid material comprises at least one chemical additive, it is in an amount adapted so that its penetrability is preferably from 5 to 50 l / 10 mm and / or the ball and ring softening temperature (TBA) is preferably greater than or equal to 60 ° C, it being understood that the penetrability is measured at 25 ° C according to EN 1426 and the TBA according to EN 1427.
Selon un premier mode de réalisation de l'invention, l'additif chimique est un composé organique. Avantageusement, le composé organique présente une masse molaire inférieure ou égale à 2000 gmol"1, de préférence une masse molaire inférieure ou égale à 1000 gmol"1. According to a first embodiment of the invention, the chemical additive is an organic compound. Advantageously, the organic compound has a molar mass less than or equal to 2000 gmol -1 , preferably a molar mass less than or equal to 1000 gmol -1 .
Dans ce premier mode de réalisation, selon une première variante, le composé organique est un composé de formule générale (I) :  In this first embodiment, according to a first variant, the organic compound is a compound of general formula (I):
Arl-R-Ar2 (I), Ar1-R-Ar2 (I),
dans laquelle : in which :
• Arl et Ar2 représentent indépendamment l'un de l'autre un noyau benzène ou un système de noyaux aromatiques condensés de 6 à 20 atomes de carbones, substitués par au moins un groupe hydroxyle, et Ar 1 and Ar 2 represent, independently of one another, a benzene ring or a fused aromatic ring system of 6 to 20 carbon atoms, substituted by at least one hydroxyl group, and
• R représente un radical divalent éventuellement substitué, dont la chaîne principale comprend de 6 à 20 atomes de carbone et au moins un groupe choisi parmi les fonctions amide, ester, hydrazide, urée, carbamate, anhydride. R represents an optionally substituted divalent radical, the main chain of which comprises from 6 to 20 carbon atoms and at least one group chosen from amide, ester, hydrazide, urea, carbamate and anhydride functions.
De préférence, Arl et/ou Ar2 sont substitués par au moins un groupe alkyle de 1 à 10 atomes de carbone, avantageusement en une ou des positions ortho par rapport au(x) groupe(s) hydroxyle(s), plus préférentiellement Arl et Ar2 sont des groupes 3,5- dialkyl-4-hydroxyphényle, avantageusement des groupes 3,5-di-tert-butyl-4- hy droxyphény le . De préférence, R est en position para par rapport à un groupe hydroxyle de Arl et/ou Ar2. Ar 1 and / or Ar 2 are preferably substituted with at least one alkyl group of 1 to 10 carbon atoms, advantageously at one or more ortho positions with respect to the hydroxyl group (s), more preferably Ar 1 and Ar 2 are 3,5-dialkyl-4-hydroxyphenyl groups, advantageously 3,5-di-tert-butyl-4-hydroxyphenyl groups. Preferably, R is in the para position with respect to a hydroxyl group of Ar1 and / or Ar2.
Avantageusement, le composé de formule (I) est le 2',3-bis[(3-[3, 5-di-tert-butyl- 4-hydroxyphenyl]propionyl)]propionohydrazide.  Advantageously, the compound of formula (I) is 2 ', 3-bis [(3- [3, 5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide.
Selon une seconde variante de ce premier mode de réalisation, le composé organique est un composé de formule générale (II) :  According to a second variant of this first embodiment, the organic compound is a compound of general formula (II):
R-(NH)nCONH-(X)m-NHCO(NH)n-R' (II), dans laquelle, R- (NH) n CONH- (X) m -NHCO (NH) n -R '(II), wherein
- les groupements R et R', identiques ou différents, contiennent une chaîne hydrocarbonée saturée ou insaturée, linéaire, ramifiée ou cyclique, comprenant de 1 à the groups R and R ', which may be identical or different, contain a saturated or unsaturated, linear, branched or cyclic hydrocarbon-based chain comprising from 1 to
22 atomes de carbone, éventuellement substituée, et comprenant éventuellement des hétéroatomes, des cycles et/ou des hétérocycles ; 22 carbon atoms, optionally substituted, and optionally comprising hetero atoms, rings and / or heterocycles;
- le groupement X contient une chaîne hydrocarbonée, saturée ou insaturée, linéaire, cyclique ou ramifiée, comprenant de 1 à 22 atomes de carbone, éventuelle- ment substituée, et comprenant éventuellement des hétéroatomes, des cycles et/ou des hétérocycles ;  the X group contains a hydrocarbon chain, saturated or unsaturated, linear, cyclic or branched, comprising from 1 to 22 carbon atoms, optionally substituted, and optionally comprising hetero atoms, rings and / or heterocycles;
- n et m sont des entiers ayant une valeur de 0 ou 1 indépendamment l'un de l'autre.  n and m are integers having a value of 0 or 1 independently of one another.
Selon cette variante, lorsque l'entier m a une valeur de 0, alors les groupements R-(NH)nCONH et NHCO(NH)n-R' sont liés de façon covalente par une liaison hydrazide CONH-NHCO. Le groupement R, ou le groupement R', comprend alors au moins un groupement choisi parmi : une chaîne hydrocarbonée d'au moins 4 atomes de carbone, un cycle aliphatique de 3 à 8 atomes, un système polycyclique condensé aliphatique, partiellement aromatique ou entièrement aromatique, chaque cycle comprenant 5 ou 6 atomes. According to this variant, when the integer ma has a value of 0, then the groups R- (NH) n CONH and NHCO (NH) n -R 'are covalently linked by a CONH-NHCO hydrazide bond. The group R, or the group R ', then comprises at least one group chosen from: a hydrocarbon chain of at least 4 carbon atoms, an aliphatic ring of 3 to 8 atoms, an aliphatic condensed polycyclic system, partially aromatic or entirely aromatic, each ring comprising 5 or 6 atoms.
Toujours selon cette variante, lorsque l'entier m a une valeur de 1, alors le groupement R, le groupement R' et/ou le groupement X, comprend au moins un groupement choisi parmi : une chaîne hydrocarbonée d'au moins 4 atomes de carbone, un cycle aliphatique de 3 à 8 atomes, un système polycyclique condensé aliphatique, partiellement aromatique ou entièrement aromatique, chaque cycle comprenant 5 ou 6 atomes. De préférence, le groupement R et/ou R' comprend une chaîne hydrocarbonée aliphatique de 4 à 22 atomes de carbone, notamment, choisie parmi les groupements C4H9, C5H11, C9H19, C11H23, C12H25, C17H35, C18H37, C21H43, C22H45. Still according to this variant, when the integer ma has a value of 1, then the group R, the group R 'and / or the group X, comprises at least one group chosen from: a hydrocarbon chain of at least 4 carbon atoms an aliphatic ring of 3 to 8 atoms, an aliphatic condensed polycyclic ring system, partially aromatic or wholly aromatic, each ring comprising 5 or 6 atoms. Preferably, the group R and / or R 'comprises an aliphatic hydrocarbon chain of 4 to 22 carbon atoms, in particular chosen from the groups C 4 H 9, C 5 H 11, C 9 H 19, C 11 H 23, C 12 H 25, C 17 H 35, C 18 H 37, C 21 H 43, C 22 H 45.
De préférence, le groupement X représente une chaîne hydrocarbonée linéaire, saturée comprenant de 1 à 22 atomes de carbone. De préférence, le groupement X est choisi parmi les groupements C2H4, C3H6.  Preferably, the group X represents a saturated linear hydrocarbon chain comprising from 1 to 22 carbon atoms. Preferably, the group X is chosen from the groups C2H4, C3H6.
De préférence, le groupement X peut aussi être un groupement cyclohexyl ou un groupement phényl, les radicaux R-(NH)nCONH- et NHCO(NH)n-R'- peuvent alors être en position ortho, méta ou para. Par ailleurs, les radicaux R-(NH)nCONH- et NHCO(NH)n-R'- peuvent être en position cis ou trans l'un par rapport à l'autre. De plus, lorsque le radical X est cyclique, ce cycle peut être substitué par d'autres groupements que les deux groupements principaux R-(NH)nCONH- et -NHCO(NH)n- R'. Preferably, the group X may also be a cyclohexyl group or a phenyl group, the radicals R- (NH) n CONH- and NHCO (NH) n -R'- may then be in the ortho, meta or para position. Moreover, the radicals R- (NH) n CONH- and NHCO (NH) n -R'- may be in the cis or trans position with respect to each other. In addition, when the radical X is cyclic, this ring may be substituted by groups other than the two main groups R- (NH) n CONH- and -NHCO (NH) n -R '.
De préférence, le groupement X comprend deux cycles de 6 carbones reliés par un groupement CH2, ces cycles étant aliphatiques ou aromatiques. Dans ce cas, le groupement X est un groupement comportant deux cycles aliphatiques reliés par un groupement C¾ éventuellement substitué comme par exemple : Preferably, the X group comprises two 6-carbon rings connected by a CH 2 group, these rings being aliphatic or aromatic. In this case, the group X is a group comprising two aliphatic rings connected by an optionally substituted C¾ group, for example:
Avantageusement, selon cette variante, le composé organique est un composé de formule générale (II) choisi parmi les dérivés hydrazides tels que les composés C5H11- CONH-NHCO-C5Hi 1, C9H19-CONH-NHCO-C9H19, Ci iH23-CONH-NHCO-Ci iH23, Ci7H35-CONH-NHCO-Ci7H35, ou C21H43-CONH-NHCO-C21H43 ; les diamides telles que la N,N*-éthylènedi(stéaramide) de formule Ci7H35-CONH-CH2-CH2-NHCO- Ci7H35 ; et les dérivés uréides tels que la 4,4'- bis(dodécylaminocarbonylamino)diphénylmethane de formule C12H25-NHCONH- C6H4-CH2-C6H4-NHCONH-Ci2H25. Advantageously, according to this embodiment, the organic compound is a compound of general formula (II) chosen from derivatives hydrazides such as compounds C5H11- CONH-NHCO-C 1 5 Hi, C9H19-CONH-C9H19-NHCO, C iH 23 - CONH-NHCO-Ci iH 23, C 7 H 3 5 -CONH-NHCO-Ci7H 35 or C21H43-CONH-NHCO-C21H43; diamides such as N, N * -éthylènedi (stearamide) of the formula Ci 7 H 35 -CONH-CH 2 CH 2 -NHCO- Ci 7 H 35; and ureide derivatives such as 4,4'-bis (dodécylaminocarbonylamino) diphenylmethane of the formula C12H25-NHCONH- C6H4-CH2-C 6 H4-NHCONH-Ci2H2 5.
De préférence, le composé de formule générale (II) est choisi parmi ceux qui satisfont à la condition n = 0. De préférence, le composé de formule générale (II) est choisi parmi ceux qui satisfont à la condition : la somme des nombres des atomes de carbone de R, X et R' est supérieur ou égal à 10, avantageusement supérieur ou égal à 14, de préférence supérieur ou égal à 18. Preferably, the compound of general formula (II) is chosen from those which satisfy the condition n = 0. Preferably, the compound of general formula (II) is chosen from those which satisfy the condition: the sum of the numbers of the carbon atoms of R, X and R 'is greater than or equal to 10, advantageously greater than or equal to 14, preferably greater than or equal to 18.
De préférence, le composé de formule générale (II) est choisi parmi ceux qui satisfont à la condition : le nombre des atomes de carbone de l'un au moins de R et R' est supérieur ou égal à 10, avantageusement supérieur ou égal à 12, de préférence supérieur ou égal à 14.  Preferably, the compound of general formula (II) is chosen from those which satisfy the condition: the number of carbon atoms of at least one of R and R 'is greater than or equal to 10, advantageously greater than or equal to 12, preferably greater than or equal to 14.
De préférence, selon une première variante, le composé de formule générale (II) est choisi parmi ceux de formule (IIA) :  Preferably, according to a first variant, the compound of general formula (II) is chosen from those of formula (IIA):
R-CONH-(X)m-NHCO-R' (IIA) R-CONH- (X) m -NHCO-R '(IIA)
dans laquelle R, R', m et X ont la même définition que ci-dessus.  wherein R, R ', m and X have the same definition as above.
De préférence, dans la formule (IIA) lorsque m= 1 , le groupement X représente une chaîne hydrocarbonée linéaire, saturée comprenant de 1 à 22 atomes de carbone, avantageusement X représente une chaîne hydrocarbonée linéaire, saturée comprenant de 1 à 12 atomes de carbone, encore mieux de 1 à 4 atomes de carbone. De préférence, le groupement X est choisi parmi les groupements C2H4, C3H6. Preferably, in the formula (IIA) when m = 1, the group X represents a saturated linear hydrocarbon-based chain containing from 1 to 22 carbon atoms, advantageously X represents a linear hydrocarbon-based saturated chain comprising from 1 to 12 carbon atoms more preferably from 1 to 4 carbon atoms. Preferably, the group X is chosen from C 2 H 4 and C 3 H 6 groups .
De préférence, le composé de formule générale (IIA) est choisi parmi ceux qui satisfont à la condition : la somme des nombres des atomes de carbone de R, X et R' est supérieur ou égal à 10, avantageusement supérieur ou égal à 14, de préférence supérieur ou égal à 18.  Preferably, the compound of general formula (IIA) is chosen from those which satisfy the condition: the sum of the numbers of the carbon atoms of R, X and R 'is greater than or equal to 10, advantageously greater than or equal to 14, preferably greater than or equal to 18.
De préférence, le composé de formule générale (IIA) est choisi parmi ceux qui satisfont à la condition : le nombre des atomes de carbone de l'un au moins de R et R' est supérieur ou égal à 10, avantageusement supérieur ou égal à 12, de préférence supérieur ou égal à 14.  Preferably, the compound of general formula (IIA) is chosen from those which satisfy the condition: the number of carbon atoms of at least one of R and R 'is greater than or equal to 10, advantageously greater than or equal to 12, preferably greater than or equal to 14.
Plus préférentiellement, selon cette variante, le composé de formule générale (IIA) est choisi parmi les dérivés hydrazides tels que les composés C5H11-CONH- NHCO-C5Hn, C9H19-CONH-NHCO-C9H19, C11H23-CONH-NHCO-C11H23, Ci7H35- CONH-NHCO-Ci7H35, ou C2iH43-CONH-NHCO-C2iH43 ; les diamides telles que le N,N*-éthylènedi(laurylamide) de formule CnH23-CONH-CH2-CH2-NHCO-CnH3i, le N,N*-éthylènedi(myristylamide) de formule Ci3H27-CONH-CH2-CH2-NHCO-Ci3H27, le N,N*-éthylènedi(palmitamide) de formule Ci5H3i-CONH-CH2-CH2-NHCO-Ci5H3i, le N,N*-éthylènedi(stéaramide) de formule Ci7H35-CONH-CH2-CH2-NHCO-Ci7H35 ; les mono amides telles que le laurylamide de formule CnH23-CONH2, le myristylamide de formule Ci3H27-CONH2, le palmitamide de formule Ci5H3i-CONH2, le stéaramide de formule Ci7H35-CONH2. More preferably, according to this variant, the compound of general formula (IIA) is selected from the hydrazide derivatives such as C5H11-CONH- compounds NHCO-C 5 H n, CONH-C9H19-NHCO-C9H19, C11H23-CONH-NHCO-C11H23 C 7 H 35 -CONH-NHCO-C 17 H 35 , or C 2 H 43 -CONH-NHCO-C 2 H 43 ; diamides such as N, N * -éthylènedi (laurylamide) of formula CnH 23 -CONH-CH 2 -CH 2 -NHCO-CnH 3 i, N, N * -éthylènedi (myristylamide) of the formula Ci 3 H 27 - CONH-CH 2 -CH 2 -NHCO-Ci 3 H 27, N, N * -éthylènedi (palmitamide) of the formula H 3 Ci 5 i-CONH-CH 2 -CH 2 -NHCO-Ci 5 H 3 i, the N, N * -éthylènedi (stearamide) of the formula Ci 7 H 35 -CONH-CH 2 -CH 2 -NHCO-Ci 7 H 35; monoamides such as laurylamide of formula CnH 2 3-CONH 2 , myristylamide of formula Ci 3 H 27 -CONH 2 , palmitamide of formula C 5 H 3 i-CONH 2 , stearamide of formula Ci 7 H 35 -CONH 2 .
De façon encore plus avantageuse, le composé de formule générale (IIA) est le N,N*-éthylènedi(stéaramide) de formule Ci7H35-CONH-CH2-CH2-NHCO-Ci7H35. Even more advantageously, the compound of general formula (IIA) is N, N '-ethylenedi (stearamide) of formula C 7 H 35 -CONH-CH 2 -CH 2 -NHCO-C 17 H 35 .
De préférence, selon une seconde variante, le composé de formule générale (II) est choisi parmi ceux de formule (IIB) :  Preferably, according to a second variant, the compound of general formula (II) is chosen from those of formula (IIB):
R-CONH-R' (IIB)  R-CONH-R '(IIB)
dans laquelle R et R' ont la même définition que ci-dessus.  in which R and R 'have the same definition as above.
Avantageusement, selon cette variante, la somme des nombres des atomes de carbone de R et R' est supérieur ou égal à 10, avantageusement supérieur ou égal à 14, de préférence supérieur ou égal à 18.  Advantageously, according to this variant, the sum of the numbers of the carbon atoms of R and R 'is greater than or equal to 10, advantageously greater than or equal to 14, preferably greater than or equal to 18.
Encore plus avantageusement, selon cette variante, le nombre des atomes de carbone de R est supérieur ou égal à 10, avantageusement supérieur ou égal à 12, de préférence supérieur ou égal à 14, et R' = H.  Even more advantageously, according to this variant, the number of carbon atoms of R is greater than or equal to 10, advantageously greater than or equal to 12, preferably greater than or equal to 14, and R '= H.
Avantageusement, le composé de formule générale (II) est choisi parmi les dérivés hydrazides tels que les composés C5H11-CONH-NHCO-C5H11 , C9H19-CONH- NHCO-C9H19, Ci iH23-CONH-NHCO-CnH23, Ci7H35-CONH-NHCO-Ci7H35, ou C2iH43-CONH-NHCO-C2iH43 ; les diamides telles que le Ν,Ν'- éthylènedi(laurylamide) de formule CnH23-CONH-CH2-CH2-NHCO-CnH3i, le Ν,Ν'- éthylènedi(myristylamide) de formule Ci3H27-CONH-CH2-CH2-NHCO-Ci3H27, le N,N*-éthylènedi(palmitamide) de formule Ci5H3i-CONH-CH2-CH2-NHCO-Ci5H3i, le N,N*-éthylènedi(stéaramide) de formule Ci7H35-CONH-CH2-CH2-NHCO-Ci7H35 ; les mono amides telles que le laurylamide de formule CnH23-CONH2, le myristylamide de formule Ci3H27-CONH2, le palmitamide de formule Ci5H3i-CONH2, le stéaramide de formule Ci7H35-CONH2. Advantageously, the compound of general formula (II) is selected from derivatives hydrazides such as C5H11-CONH-C5H11-NHCO compounds, C9H19-CONH NHCO-C9H19, C iH 23 -CONH-NHCO-C n H 23, C 7 H 35 -CONH-NHCO-Ci 7 H 35, or C 2 iH 43 -CONH-NHCO-C 2 iH 43; diamides such as Ν, Ν'-ethylenedi (laurylamide) of formula C n H 23 -CONH-CH 2 -CH 2 -NHCO-C nH 3 i, Ν, Ν'-ethylenedi (myristylamide) of formula Ci 3 H 27 - CONH-CH 2 -CH 2 -NHCO-C 3 H 27 , N, N'-ethylenedi (palmitamide) of formula Ci 5 H 3 i-CONH-CH 2 -CH 2 -NHCO-Ci 5 H 3 i, N, N '-ethylenedi (stearamide) of the formula C 7 H 35 -CONH-CH 2 -CH 2 -NHCO-C 17 H 35 ; monoamides such as laurylamide of formula CnH 23 -CONH 2 , myristylamide of formula Ci 3 H 27 -CONH 2 , palmitamide of formula Ci 5 H 3 i-CONH 2 , stearamide of formula Ci 7 H 35 -CONH 2 .
De façon encore plus avantageuse, le composé de formule générale (II) est le N,N*-éthylènedi(stéaramide) de formule Ci7H35-CONH-CH2-CH2-NHCO-Ci7H35. Even more advantageously, the compound of general formula (II) is N, N * -ethylenedi (stearamide) of formula C 7 H 35 -CONH-CH 2 -CH 2 -NHCO-C 17 H 35 .
De préférence, lorsque l'additif chimique est choisi parmi les composés organiques de formule (II), il est utilisé en combinaison avec au moins un autre additif chimique choisi parmi les composés organiques de formule (I), (III), (V), (VI) et (VII) et/ou les produits de réaction d'au moins un polyol en C3-C12 et d'au moins un aldéhyde en C2-C12, notamment ceux comprenant un groupement de formule (IV). Selon une troisième variante de ce mode de réalisation, le composé organique est un composé de formule (III) : Preferably, when the chemical additive is chosen from the organic compounds of formula (II), it is used in combination with at least one other chemical additive chosen from the organic compounds of formula (I), (III), (V) , (VI) and (VII) and / or the reaction products of at least one C3-C12 polyol and at least one C2-C12 aldehyde, in particular those comprising a group of formula (IV). According to a third variant of this embodiment, the organic compound is a compound of formula (III):
(R-NHCO)x-Z-(NHCO-R')y (III), (R-NHCO) x -Z- (NHCO-R ') y (III),
dans laquelle,  in which,
- R et R', identiques ou différents, contiennent une chaîne hydrocarbonée saturée ou insaturée, linéaire, ramifiée ou cyclique comprenant de 1 à 22 atomes de carbone, éventuellement substituée, et éventuellement comprenant des hétéroatomes, des cycles et/ou des hétérocycles,  - R and R ', which may be identical or different, contain a linear, branched or cyclic saturated or unsaturated hydrocarbon-based chain containing from 1 to 22 carbon atoms, which may be optionally substituted, and optionally comprising hetero atoms, rings and / or heterocycles,
- Z représente un groupement tri-fonctionnalisé choisi parmi les groupements suivants :  Z represents a tri-functionalized group chosen from the following groups:
- x et y sont des entiers différents de valeur variant de 0 à 3 et tels que x+y=3. De préférence, lorsque x est égal à 0 et Z représente Z2, le composé de formule (III) est la N2, N4, N6-tridécylmélamine ayant la formule suivante avec R' représentant le groupe C9H19 : x and y are different integers with values ranging from 0 to 3 and such that x + y = 3. Preferably, when x is 0 and Z is Z 2 , the compound of formula (III) is N 2, N 4, N 6 -tridecylmelamine having the following formula with R 'representing the group C 9 H 19:
D'autres composés préférés répondant à la formule (III), sont tels que x est égal à 0, Z représente Z2 et R' représente une chaîne hydrocarbonée saturée, linéaire, de 1 à 22 atomes de carbone, de préférence de 2 à 18 atomes de carbone, de préférence de 5 à 12 atomes de carbone. Other preferred compounds corresponding to formula (III) are such that x is equal to 0, Z represents Z 2 and R 'represents a linear saturated hydrocarbon-based chain of 1 to 22 carbon atoms, preferably 2 to 18 carbon atoms, preferably 5 to 12 carbon atoms.
D'autres composés préférés répondant à la formule (III) sont tels que : y est égal à 0 et Z représente Zl s les composés ont alors pour formule : Other preferred compounds corresponding to formula (III) are such that: y is 0 and Z is Z ls the compounds then have the formula:
avec R choisi parmi les groupes suivants, pris seuls ou en mélanges with R selected from the following groups, taken alone or in mixtures
D'autres composés préférés répondant à la formule (III) sont tels que : y est égal à 0, Z représente Z\ et R représente une chaîne hydrocarbonée saturée, linéaire, de 1 à 22 atomes de carbone, de préférence de 8 à 12 atomes de carbone. Other preferred compounds corresponding to formula (III) are such that: y is 0, Z represents Z 1 and R represents a linear saturated hydrocarbon-based chain of 1 to 22 carbon atoms, preferably 8 to 12 carbon atoms. carbon atoms.
Selon une quatrième variante de ce mode de réalisation, le composé organique est un produit de réaction d'au moins un polyol en C3-C12 et d'au moins un aldéhyde en C2-C 12. Parmi les polyols utilisables, on peut citer le sorbitol, le xylitol, le mannitol et/ou le ribitol. De préférence, le polyol est le sorbitol.  According to a fourth variant of this embodiment, the organic compound is a reaction product of at least one C 3 -C 12 polyol and at least one C 2 -C 12 aldehyde. Among the polyols that may be used, mention may be made of sorbitol, xylitol, mannitol and / or ribitol. Preferably, the polyol is sorbitol.
Avantageusement, selon cette variante, le composé organique est un composé qui comprend au moins une fonction de formule générale (IV) :  Advantageously, according to this variant, the organic compound is a compound which comprises at least one function of general formula (IV):
(IV)  (IV)
Avec :  With:
- x est un entier,  - x is an integer,
- R est choisi parmi un radical alkyle, alcényle, aryle, ou aralkyle en Cl -C l l , éventuellement substitué par un ou plusieurs atomes d'halogène, un ou plusieurs groupements alcoxy en C1-C6.  - R is chosen from a C 1 -C 11 alkyl, alkenyl, aryl or aralkyl radical, optionally substituted by one or more halogen atoms, or one or more C 1 -C 6 alkoxy groups.
Le composé organique est avantageusement un dérivé du sorbitol. Par « dérivé du sorbitol », on entend tout produit de réaction, obtenu à partir du sorbitol. En particulier, tout produit de réaction obtenu en faisant réagir un aldéhyde avec du D- sorbitol. On obtient par cette réaction de condensation, des acétals de sorbitol, qui sont des dérivés du sorbitol. Le l,3:2,4-Di-0-benzylidène-D-sorbitol est obtenu en faisant réagir 1 mole de D-sorbitol et 2 moles de benzaldéhyde et a pour formule : The organic compound is advantageously a derivative of sorbitol. By "sorbitol derivative" is meant any reaction product, obtained from sorbitol. In particularly, any reaction product obtained by reacting an aldehyde with D-sorbitol. This condensation reaction produces sorbitol acetals, which are derivatives of sorbitol. 1,3: 2,4-Di-O-benzylidene-D-sorbitol is obtained by reacting 1 mole of D-sorbitol and 2 moles of benzaldehyde and has the formula:
Les dérivés du sorbitol pourront ainsi être tous les produits de condensation d'aldéhydes, notamment d'aldéhydes aromatiques avec le sorbitol. On obtiendra alors des dérivés du sorbitol de formule générale :  The sorbitol derivatives may thus be all the condensation products of aldehydes, especially aromatic aldehydes with sorbitol. Sorbitol derivatives of general formula will then be obtained:
où Ari et Ar2 sont des noyaux aromatiques éventuellement substitués. where Ari and Ar 2 are optionally substituted aromatic rings.
Parmi les dérivés du sorbitol, autre que le l,3:2,4-Di-0-benzylidene-D-sorbitol on peut trouver par exemple le l,3:2,4:5,6-tri-0-benzylidene-D-sorbitol, le 2,4-mono- O-benzylidene-D-sorbitol, le l,3:2,4-bis(p-methylbenzylidene) sorbitol, 1,3:2,4- bis(3,4-dimethylbenzylidene) sorbitol, l,3:2,4-bis(p-ethylbenzylidene) sorbitol, l,3:2,4-bis(p-propylbenzylidene) sorbitol, l,3:2,4-bis(p-butylbenzylidene) sorbitol, l,3:2,4-bis(p-ethoxylbenzylidene) sorbitol, l,3:2,4-bis(p-chlorobenzylidene) sorbitol, 1 ,3 :2,4-bis(p-bromobenzylidene) sorbitol, 1 ,3 :2,4-Di-0-methylbenzylidene-D- sorbitol, 1 ,3 :2,4-Di-0-dimethylbenzylidene-D-sorbitol, 1 ,3 :2,4-Di-0-(4- methylbenzylidene)-D-sorbitol, 1 ,3 :2,4-Di-0-(4,3-dimethylbenzylidene)-D-sorbitol. De préférence, selon cette variante, le composé organique est le l,3:2,4-Di-0- benzylidene -D-sorbitol.  Among the derivatives of sorbitol, other than 1,3: 2,4-Di-O-benzylidene-D-sorbitol, there can be found, for example, 1,3,3,4,5,6-tri-O-benzylidene- D-sorbitol, 2,4-mono-O-benzylidene-D-sorbitol, 1,3: 2,4-bis (p-methylbenzylidene) sorbitol, 1,3: 2,4-bis (3,4-bis), dimethylbenzylidene) sorbitol, 1,3,2,4-bis (p-ethylbenzylidene) sorbitol, 1,3,2,4-bis (p-propylbenzylidene) sorbitol, 1,3,2,4-bis (p-butylbenzylidene) sorbitol, 1,3,2,4-bis (p-ethoxylbenzylidene) sorbitol, 1,3,2,4-bis (p-chlorobenzylidene) sorbitol, 1,3,2,4-bis (p-bromobenzylidene) sorbitol, 1, 3: 2,4-Di-O-methylbenzylidene-D-sorbitol, 1: 3: 2,4-Di-O-dimethylbenzylidene-D-sorbitol, 1: 3: 2,4-Di-O- (4) methylbenzylidene) -D-sorbitol, 1, 3: 2,4-Di-O- (4,3-dimethylbenzylidene) -D-sorbitol. Preferably, according to this variant, the organic compound is 1,3,3,4-Di-O-benzylidene-D-sorbitol.
Selon une cinquième variante de ce mode de réalisation, le composé organique est un composé de formule générale (V) : R"-(COOH)z (V), According to a fifth variant of this embodiment, the organic compound is a compound of general formula (V): R "- (COOH) z (V),
dans laquelle R" représente une chaîne linéaire ou ramifiée, saturée ou insaturée comprenant de 4 à 68 atomes de carbone, de préférence de 4 à 54 atomes de carbone, plus préférentiellement de 4 à 36 atomes de carbone et z est un entier variant de 2 à 4.  in which R "represents a linear or branched, saturated or unsaturated chain comprising from 4 to 68 carbon atoms, preferably from 4 to 54 carbon atoms, more preferably from 4 to 36 carbon atoms, and z is an integer ranging from 2 to at 4.
De préférence, le groupement R' ' est de préférence, une chaîne linéaire saturée de formule CwH2w avec w un entier variant de 4 à 22, de préférence de 4 à 12. Preferably, the group R '' is preferably a saturated linear chain of formula C w H 2w with w an integer ranging from 4 to 22, preferably from 4 to 12.
Selon cette variante de l'invention, les composés organiques répondant à la formule (V) peuvent être des diacides (z = 2), des triacides (z = 3) ou des tétracides (z = 4). Les composés organiques préférés selon cette variante, sont des diacides avec z = 2.  According to this variant of the invention, the organic compounds corresponding to the formula (V) may be diacids (z = 2), triacids (z = 3) or tetracides (z = 4). The preferred organic compounds according to this variant are diacids with z = 2.
De préférence, selon cette variante, les diacides ont pour formule générale HOOC-CwH2w-COOH avec w un entier variant de 4 à 22, de préférence de 4 à 12 et où z = 2 et R" = CwH2w. Preferably, according to this variant, the diacids have the general formula HOOC-C w H 2w -COOH with w an integer ranging from 4 to 22, preferably from 4 to 12 and where z = 2 and R "= C w H 2w .
Avantageusement, selon cette variante, le composé organique est un diacide choisi parmi l'acide adipique ou acide 1,6-hexanedioïque avec w = 4, l'acide pimélique ou acide 1 ,7-heptanedioïque avec w = 5, l'acide subérique ou acide 1,8- octanedioïque avec w = 6, l'acide azélaique ou acide 1,9-nonanedioïque avec w = 7, l'acide sébacique ou acide 1,10-décanedioïque avec w = 8, l'acide undécanedioïque avec w = 9, l'acide 1 ,2-dodécanedioïque avec w = 10 ou l'acide tétradécanedioïque avec w = 12.  Advantageously, according to this variant, the organic compound is a diacid chosen from adipic acid or 1,6-hexanedioic acid with w = 4, pimelic acid or 1, 7-heptanedioic acid with w = 5, and suberic acid or 1,8-octanedioic acid with w = 6, azelaic acid or 1,9-nonanedioic acid with w = 7, sebacic acid or 1,10-decanedioic acid with w = 8, undecanedioic acid with w = 9, 1, 2-dodecanedioic acid with w = 10 or tetradecanedioic acid with w = 12.
Avantageusement, le diacide est l'acide sébacique.  Advantageously, the diacid is sebacic acid.
Les diacides peuvent aussi être des dimères diacides d'acide(s) gras insaturé(s) c'est-à-dire des dimères formés à partir d'au moins un acide gras insaturé, par exemple à partir d'un seul acide gras insaturé ou à partir de deux acides gras insaturés différents. Les dimères diacides d'acide(s) gras insaturé(s) sont classiquement obtenus par réaction de dimérisation intermoléculaire d'au moins un acide gras insaturé (réaction de Diels Aider par exemple). De préférence, on dimérise un seul type d'acide gras insaturé. Ils dérivent en particulier de la dimérisation d'un acide gras insaturé notamment en Cs à C34, notamment en C12 à C22, en particulier en C16 à C2o, et plus particulièrement en C18. Un dimère d'acide gras préféré est obtenu par dimérisation de l'acide linoléïque, celui-ci pouvant ensuite être partiellement ou totalement hydrogéné. Un autre dimère d'acide gras préféré a pour formule HOOC- (CH2)7-CH=CH-(CH2)7-COOH. Un autre dimère d'acide gras préféré est obtenu par dimérisation du linoléate de méthyle. De la même façon, on peut trouver des triacides d'acides gras et des tétracides d'acides gras, obtenus respectivement par trimérisation et tétramérisation d'au moins un acide gras. The diacids may also be diacid dimers of unsaturated fatty acid (s), that is to say dimers formed from at least one unsaturated fatty acid, for example from a single fatty acid. unsaturated or from two different unsaturated fatty acids. The diacid dimers of unsaturated fatty acid (s) are conventionally obtained by intermolecular dimerization reaction of at least one unsaturated fatty acid (reaction of Diels Aid for example). Preferably, only one type of unsaturated fatty acid is dimerized. They derive in particular from the dimerization of an unsaturated fatty acid, in particular C 6 to C 34, especially C 12 to C 22 , in particular C 16 to C 20 , and more particularly C 18 . A preferred fatty acid dimer is obtained by dimerization of linoleic acid, which can then be partially or fully hydrogenated. Another preferred fatty acid dimer has the formula HOOC- (CH 2 ) 7-CH = CH- (CH 2 ) 7 -COOH. Another preferred fatty acid dimer is obtained by dimerization of methyl linoleate. In the same way, it is possible to find triacids of fatty acids and tetracides of fatty acids, obtained respectively by trimerization and tetramerization of at least one fatty acid.
Selon une sixième variante de ce mode de réalisation, le composé organique est un composé de formule générale (VI) :  According to a sixth variant of this embodiment, the organic compound is a compound of general formula (VI):
^ (CH2)p ^ ^ (CH 2 ) p ^
O O
(VI) dans laquelle,  (VI) wherein,
les groupements Y et Y' représentent indépendamment l'un de l'autre, un atome ou groupement choisi parmi : H, -(CH2)q-CH3, -(CH2)q-NH2, -(CH2)q- OH, -(CH2)q-COOH ou the groups Y and Y 'represent, independently of one another, an atom or a group chosen from: H, - (CH 2 ) q -CH 3 , - (CH 2 ) q -NH 2 , - (CH 2 ) q- OH, - (CH 2 ) q-COOH or
. (CH2 . (CH 2
avec q un entier variant de 2 à 18, de préférence de 2 à 10, de préférence de 2 à 4 et p un entier supérieur ou égal à 2, de préférence ayant une valeur de 2 ou 3. with q an integer varying from 2 to 18, preferably from 2 to 10, preferably from 2 to 4 and p an integer greater than or equal to 2, preferably having a value of 2 or 3.
Parmi les composés organiques préférés répondant à la formule (VI), on peut citer les composés suivants : Among the preferred organic compounds of formula (VI), there may be mentioned the following compounds:
De préférence, selon cette variante, le composé organique de formule générale Preferably, according to this variant, the organic compound of general formula
Selon une septième variante de ce mode de réalisation, le composé organique est un composé de formule générale (VII) : R-NH-CO-CO-NH-R' (VII) According to a seventh variant of this embodiment, the organic compound is a compound of general formula (VII): R-NH-CO-CO-NH-R '(VII)
dans laquelle, R et R', identiques ou différents, représentent une chaîne hydrocarbonée saturée ou insaturée, linéaire, ramifiée ou cyclique, comprenant de 1 à 22 atomes de carbone, de préférence de 8 à 12 atomes de carbone, éventuellement substituée, et comprenant éventuellement des hétéroatomes, des cycles et/ou des hétérocycles.  in which R and R ', which may be identical or different, represent a saturated or unsaturated, linear, branched or cyclic hydrocarbon-based chain comprising from 1 to 22 carbon atoms, preferably from 8 to 12 carbon atoms, which may be substituted, and comprising optionally heteroatoms, rings and / or heterocycles.
Selon un autre mode de réalisation de l'invention, l'additif chimique est une paraffine. Les paraffines présentent des longueurs de chaînes de 30 à 120 atomes de carbone (C30 à Ci 20). Les paraffines sont avantageusement choisies parmi les polyalkylènes. De préférence, on utilisera selon l'invention des paraffines de polyméthylène et des paraffines de polyéthylène. Ces paraffines pourront être d'origine pétrolière ou provenir de l'industrie chimique. Avantageusement, les paraffines utilisées sont des paraffines synthétiques issues de la conversion de la biomasse et/ou du gaz naturel. According to another embodiment of the invention, the chemical additive is a paraffin. Paraffins have chain lengths of 30 to 120 carbon atoms (C 30 to C 20). The paraffins are advantageously chosen from polyalkylenes. Preferably, polymethylene paraffins and polyethylene paraffins will be used according to the invention. These paraffins may be of petroleum origin or come from the chemical industry. Advantageously, paraffins used are synthetic paraffins resulting from the conversion of biomass and / or natural gas.
De préférence, ces paraffines contiennent une grande proportion de paraffines dites « normales » c'est-à-dire de paraffines linéaires à chaîne droite, non ramifiées (hydrocarbures saturés). Ainsi, les paraffines peuvent comprendre de 50 à 100% de paraffines normales et de 0 à 50% d'isoparaffines et/ou de paraffines ramifiées. Plus préférentiellement, les paraffines comprennent de 85 à 95% de paraffines normales et de 5 à 15%) d'isoparaffines et/ou de paraffines ramifiées. Avantageusement, les paraffines comprennent de 50 à 100% de paraffines normales et de 0 à 50% d'isoparaffines. Encore plus avantageusement, les paraffines comprennent de 85 à 95%) de paraffines normales et de 5 à 15% d'isoparaffines.  Preferably, these paraffins contain a large proportion of so-called "normal" paraffins, that is straight-chain, unbranched linear paraffins (saturated hydrocarbons). Thus, the paraffins may comprise from 50 to 100% of normal paraffins and from 0 to 50% of isoparaffins and / or branched paraffins. More preferably, the paraffins comprise 85 to 95% of normal paraffins and 5 to 15%) of isoparaffins and / or branched paraffins. Advantageously, the paraffins comprise from 50 to 100% of normal paraffins and from 0 to 50% of isoparaffins. Even more preferably, the paraffins comprise from 85 to 95% of normal paraffins and from 5 to 15% of isoparaffins.
De préférence, les paraffines sont des paraffines de polyméthylène. Plus particulièrement, les paraffines sont des paraffines synthétiques de polyméthylène, par exemple des paraffines issues de la conversion de gaz de synthèse par le procédé Fischer-Tropsch. Dans le procédé Fischer-Tropsch, les paraffines sont obtenues par réaction de l'hydrogène avec de l'oxyde de carbone sur un catalyseur métallique. Des procédés de synthèse Fischer-Tropsch sont décrits par exemple dans les publications EP 1 432 778, EP 1 328 607 ou EP 0 199 475.  Preferably, the paraffins are polymethylene paraffins. More particularly, paraffins are synthetic paraffins of polymethylene, for example paraffins resulting from the conversion of synthesis gas by the Fischer-Tropsch process. In the Fischer-Tropsch process, paraffins are obtained by reaction of hydrogen with carbon monoxide on a metal catalyst. Fischer-Tropsch synthesis methods are described for example in the publications EP 1 432 778, EP 1 328 607 or EP 0 199 475.
Selon un autre mode de réalisation de l'invention, l'additif chimique est un acide polyphosphorique. Les acides polyphosphoriques (PPA) utilisables dans l'invention sont décrits dans WO 97/14753. Ce sont des composés de formule brute PqHrOs dans laquelle q, r et s sont des nombres positifs tels que :  According to another embodiment of the invention, the chemical additive is a polyphosphoric acid. The polyphosphoric acids (PPA) that can be used in the invention are described in WO 97/14753. These are compounds of the formula PqHrOs in which q, r and s are positive numbers such that:
q > 2 et notamment q va de 3 à 20 ou plus et que 5q+r-2s=0. q> 2 and in particular q is from 3 to 20 or more and that 5q + r-2s = 0.
En particulier, lesdits acides polyphosphoriques peuvent être des composés linéaires de formule brute PqH(q+2)0(3q+i) correspondant à la formule développée : In particular, said polyphosphoric acids may be linear compounds of formula P q H (q + 2) O (3q + 1) corresponding to the structural formula:
Où q a la définition donnée ci-dessus. Ils peuvent encore être des produits de structure bidimensionnelle ou tridimensionnelle. Where q has the definition given above. They can still be products of two-dimensional or three-dimensional structure.
Tous ces acides polyphosphoriques peuvent être considérés comme des produits de polycondensation par chauffage de l'acide métaphosphorique aqueux. On ne sortira pas du cadre de l'invention en combinant plusieurs additifs chimiques différents tels que différents composés organiques de formule (I), (II), (III), (V), (VI) et (VII), les produits de réaction d'au moins un polyol en C3-C12 et d'au moins un aldéhyde en C2-C12, notamment ceux comprenant un groupement de formule (IV), et/ou différentes paraffines et/ou différents acides polyphosphoriques dans la base bitume. All these polyphosphoric acids can be considered as polycondensation products by heating aqueous metaphosphoric acid. It will not be departing from the scope of the invention by combining several different chemical additives such as various organic compounds of formula (I), (II), (III), (V), (VI) and (VII), the products of reacting at least one C3-C12 polyol and at least one C2-C12 aldehyde, in particular those comprising a group of formula (IV), and / or different paraffins and / or various polyphosphoric acids in the bitumen base.
Selon un mode de réalisation de l'invention, la première composition, comprenant une base bitume, dont est composé le cœur des granules comprend de 0,1% à 10% en masse, de préférence de 0,5%> à 5% en masse, plus préférentiellement de 0,5%) à 2,5% en masse d'additif chimique par rapport à la masse totale de la première composition.  According to one embodiment of the invention, the first composition, comprising a bitumen base, of which the core of the granules is composed comprises from 0.1% to 10% by weight, preferably from 0.5% to 5% by weight. mass, more preferably 0.5%) to 2.5% by weight of chemical additive relative to the total mass of the first composition.
Selon un mode de réalisation avantageux, la première composition comprend au moins deux additifs chimiques.  According to an advantageous embodiment, the first composition comprises at least two chemical additives.
Selon une première variante de ce mode de réalisation, la première composition comprend au moins un premier additif chimique de formule (V) et au moins un second additif chimique choisi parmi : les additifs chimiques de formule (I) ; les additifs chimiques de formule (II) ; les additifs chimiques de formule (III) ; les additifs chimiques de formule (V) ; les additifs chimiques de formule (VI) ; les additifs chimiques de formule (VII) et les produits de réaction d'au moins un polyol en C3- C12 et d'au moins un aldéhyde en C2-C12, notamment ceux comprenant un groupement de formule (IV), le second additif chimique étant distinct du premier additif chimique.  According to a first variant of this embodiment, the first composition comprises at least one first chemical additive of formula (V) and at least one second chemical additive chosen from: chemical additives of formula (I); chemical additives of formula (II); chemical additives of formula (III); chemical additives of formula (V); chemical additives of formula (VI); the chemical additives of formula (VII) and the reaction products of at least one C 3 -C 12 polyol and at least one C 2 -C 12 aldehyde, in particular those comprising a group of formula (IV), the second chemical additive being distinct from the first chemical additive.
De préférence, et selon cette première variante, la première composition comprend au moins un premier additif chimique de formule (V) et au moins un second additif chimique de formule (II).  Preferably, and according to this first variant, the first composition comprises at least one first chemical additive of formula (V) and at least one second chemical additive of formula (II).
Plus préférentiellement, et selon cette première variante, la première composition comprend au moins un premier additif de formule (V) et au moins un second additif chimique de formule (IIA).  More preferably, and according to this first variant, the first composition comprises at least one first additive of formula (V) and at least one second chemical additive of formula (IIA).
De préférence, et toujours selon cette première variante, le premier additif chimique de formule (V) est choisi parmi les diacides (z=2), les triacides (z=3) et les tétracides (z=4), de préférence parmi les diacides (z=2).  Preferably, and still according to this first variant, the first chemical additive of formula (V) is chosen from diacids (z = 2), triacids (z = 3) and tetracides (z = 4), preferably from diacids (z = 2).
Plus préférentiellement, et toujours selon cette première variante, le premier additif chimique de formule (V) est choisi parmi l'acide adipique ou acide 1,6- hexanedioïque avec w = 4, l'acide pimélique ou acide 1,7-heptanedioïque avec w = 5, l'acide subérique ou acide 1,8-octanedioïque avec w = 6, l'acide azélaique ou acide 1,9-nonanedioïque avec w = 7, l'acide sébacique ou acide 1,10-décanedioïque avec w = 8, l'acide undécanedioïque avec w = 9, l'acide 1 ,2-dodécanedioïque avec w = 10 ou l'acide tétradécanedioïque avec w = 12. More preferably, and still according to this first variant, the first chemical additive of formula (V) is chosen from adipic acid or 1,6- hexanedioic acid with w = 4, pimelic acid or 1,7-heptanedioic acid with w = 5, suberic acid or 1,8-octanedioic acid with w = 6, azelaic acid or 1,9-nonanedioic acid with w = 7, sebacic acid or 1,10-decanedioic acid with w = 8, undecanedioic acid with w = 9, 1,2-dodecanedioic acid with w = 10 or tetradecanedioic acid with w = 12 .
Avantageusement, et selon cette première variante, le premier additif chimique de formule (V) est l'acide sébacique ou acide 1,10-décanedioïque avec w = 8.  Advantageously, and according to this first variant, the first chemical additive of formula (V) is sebacic acid or 1,10-decanedioic acid with w = 8.
Selon une seconde variante de ce mode réalisation, la première composition comprend au moins un premier additif chimique de formule (II) et au moins un second additif chimique choisi parmi : les additifs chimiques de formule (I) ; les additifs chimiques de formule (II) ; les additifs chimiques de formule (III) ; les additifs chimiques de formule (V) ; les additifs chimiques de formule (VI) ; les additifs chimiques de formule (VII) et les produits de réaction d'au moins un polyol en C3- C12 et d'au moins un aldéhyde en C2-C12, notamment ceux comprenant un groupement de formule (IV), le second additif chimique étant distinct du premier additif chimique.  According to a second variant of this embodiment, the first composition comprises at least one first chemical additive of formula (II) and at least one second chemical additive chosen from: chemical additives of formula (I); chemical additives of formula (II); chemical additives of formula (III); chemical additives of formula (V); chemical additives of formula (VI); the chemical additives of formula (VII) and the reaction products of at least one C 3 -C 12 polyol and at least one C 2 -C 12 aldehyde, in particular those comprising a group of formula (IV), the second chemical additive being distinct from the first chemical additive.
De préférence, et selon cette seconde variante, le premier additif chimique de formule (II) est choisi parmi les additifs chimiques de formule (IIA).  Preferably, and according to this second variant, the first chemical additive of formula (II) is chosen from the chemical additives of formula (IIA).
Plus préférentiellement, et selon cette seconde variante, la première composition comprend au moins un premier additif chimique de formule (IIA) et au moins un second additif chimique choisi parmi : les additifs chimiques de formule (I) ; les additifs chimiques de formule (IIB) ; les additifs chimiques de formule (III) ; les additifs chimiques de formule (V) ; les additifs chimiques de formule (VI) ; les additifs chimiques de formule (VII) et les produits de réaction d'au moins un polyol en C3-C12 et d'au moins un aldéhyde en C2-C12, notamment ceux comprenant un groupement de formule (IV), le second additif chimique étant distinct du premier additif chimique.  More preferably, and according to this second variant, the first composition comprises at least one first chemical additive of formula (IIA) and at least one second chemical additive chosen from: chemical additives of formula (I); chemical additives of formula (IIB); chemical additives of formula (III); chemical additives of formula (V); chemical additives of formula (VI); the chemical additives of formula (VII) and the reaction products of at least one C 3 -C 12 polyol and at least one C 2 -C 12 aldehyde, in particular those comprising a group of formula (IV), the second chemical additive being distinct from the first chemical additive.
Encore plus préférentiellement, et selon cette seconde variante, la première composition comprend au moins un premier additif de formule (IIA) et au moins un second additif de formule (V).  Even more preferentially, and according to this second variant, the first composition comprises at least one first additive of formula (IIA) and at least one second additive of formula (V).
Avantageusement, et selon cette seconde variante, le premier additif chimique de formule (II) est le N,N'-éthylènedi(stéaramide). Selon une troisième variante préférée de ce mode de réalisation, la première composition comprend au moins de l'acide sébacique ou acide 1,10-décanedioïque et au moins du N,N'-éthylènedi(stéaramide). Advantageously, and according to this second variant, the first chemical additive of formula (II) is N, N'-ethylenedi (stearamide). According to a third preferred variant of this embodiment, the first composition comprises at least sebacic acid or 1,10-decanedioic acid and at least N, N'-ethylenedi (stearamide).
Selon une quatrième variante de ce mode de réalisation, la première composition comprend au moins un premier additif de formule (I) et au moins un second additif chimique choisi parmi : les additifs chimiques de formule (I) ; les additifs chimiques de formule (II) ; les additifs chimiques de formule (III) ; les additifs chimiques de formule (V) ; les additifs chimiques de formule (VI) ; les additifs chimiques de formule (VII) et les produits de réaction d'au moins un polyol en C3-C12 et d'au moins un aldéhyde en C2-C12, notamment ceux comprenant un groupement de formule (IV), le second additif chimique étant distinct du premier additif chimique.  According to a fourth variant of this embodiment, the first composition comprises at least one first additive of formula (I) and at least one second chemical additive chosen from: chemical additives of formula (I); chemical additives of formula (II); chemical additives of formula (III); chemical additives of formula (V); chemical additives of formula (VI); the chemical additives of formula (VII) and the reaction products of at least one C 3 -C 12 polyol and at least one C 2 -C 12 aldehyde, in particular those comprising a group of formula (IV), the second chemical additive being distinct from the first chemical additive.
De préférence, et selon cette quatrième variante, le second additif chimique est choisi parmi les additifs chimiques de formule (II) et les additifs chimiques de formule (V).  Preferably, and according to this fourth variant, the second chemical additive is chosen from the chemical additives of formula (II) and the chemical additives of formula (V).
De préférence, et selon cette quatrième variante, le second additif chimique de formule (II) est choisi parmi les additifs chimiques de formule (II A).  Preferably, and according to this fourth variant, the second chemical additive of formula (II) is chosen from the chemical additives of formula (II A).
Plus préférentiellement, et selon cette quatrième variante, le second additif chimique de formule (II) est le N,N'-éthylènedi(stéaramide).  More preferably, and according to this fourth variant, the second chemical additive of formula (II) is N, N'-ethylenedi (stearamide).
De préférence, et toujours selon cette quatrième variante, le second additif chimique de formule (V) est choisi parmi les diacides (z=2), les triacides (z=3) et les tétracides (z=4), de préférence parmi les diacides (z=2).  Preferably, and still according to this fourth variant, the second chemical additive of formula (V) is chosen from diacids (z = 2), triacids (z = 3) and tetracides (z = 4), preferably from diacids (z = 2).
Encore plus préférentiellement, et toujours selon cette quatrième variante, le second additif chimique de formule (V) est choisi parmi l'acide adipique ou acide 1,6- hexanedioïque avec w = 4, l'acide pimélique ou acide 1,7-heptanedioïque avec w = 5, l'acide subérique ou acide 1,8-octanedioïque avec w = 6, l'acide azélaique ou acide 1,9-nonanedioïque avec w = 7, l'acide sébacique ou acide 1,10-décanedioïque avec w = 8, l'acide undécanedioïque avec w = 9, l'acide 1 ,2-dodécanedioïque avec w = 10 ou l'acide tétradécanedioïque avec w = 12.  Even more preferentially, and still according to this fourth variant, the second chemical additive of formula (V) is chosen from adipic acid or 1,6-hexanedioic acid with w = 4, pimelic acid or 1,7-heptanedioic acid with w = 5, suberic acid or 1,8-octanedioic acid with w = 6, azelaic acid or 1,9-nonanedioic acid with w = 7, sebacic acid or 1,10-decanedioic acid with w = 8, undecanedioic acid with w = 9, 1, 2-dodecanedioic acid with w = 10 or tetradecanedioic acid with w = 12.
Avantageusement, et toujours selon cette quatrième variante, le second additif chimique de formule (V) est l'acide sébacique ou acide 1,10-décanedioïque.  Advantageously, and still according to this fourth variant, the second chemical additive of formula (V) is sebacic acid or 1,10-decanedioic acid.
De préférence, et selon cette quatrième variante, le premier additif chimique de formule (I) est le 2',3-bis[(3-[3, 5-di-tert-butyl-4- hydroxyphenyl]propionyl)]propionohydrazide. De préférence, et selon ce mode de réalisation, le ratio massique du premier additif chimique par rapport au second additif chimique est de 1 : 99 à 99 : 1 , de préférence de 1 :9 à 9 : 1 , encore plus préférentiellement de 1 :5 à 5 : 1. Adjuvant polymère oléfinique Preferably, and according to this fourth variant, the first chemical additive of formula (I) is 2 ', 3-bis [(3- [3, 5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide. Preferably, and according to this embodiment, the mass ratio of the first chemical additive with respect to the second chemical additive is from 1: 99 to 99: 1, preferably from 1: 9 to 9: 1, even more preferably from 1: 5 to 5: 1. olefinic polymer adjuvant
Selon un mode de réalisation de l'invention, la première composition peut en outre comprendre au moins un adjuvant polymère oléfinique.  According to one embodiment of the invention, the first composition may further comprise at least one olefinic polymer adjuvant.
L'adjuvant polymère oléfinique est choisi, de préférence, dans le groupe consistant en (a) les copolymères éthylène/(méth)acrylate de glycidyle ; (b) les terpolymères éthylène/monomère A/monomère B et (c) les copolymères résultant du greffage d'un monomère B sur un substrat polymère.  The olefin polymer adjuvant is preferably selected from the group consisting of (a) ethylene / glycidyl (meth) acrylate copolymers; (b) ethylene / monomer A / monomer B terpolymers and (c) copolymers resulting from the grafting of a monomer B onto a polymer substrate.
(a) Les copolymères éthylène/(méth)acrylate de glycidyle sont, avantageusement, choisis parmi les copolymères statistiques ou séquencés, de préférence statistiques, d'éthylène et d'un monomère choisi parmi l'acrylate de glycidyle et le méthacrylate de glycidyle, comprenant de 50% à 99,7% en masse, de préférence de 60%> à 95% en masse, plus préférentiellement 60% à 90% en masse d'éthylène. (a) The ethylene / glycidyl (meth) acrylate copolymers are advantageously chosen from random or block copolymers, preferably random copolymers of ethylene and a monomer chosen from glycidyl acrylate and glycidyl methacrylate, comprising from 50% to 99.7% by weight, preferably from 60% to 95% by weight, more preferably 60% to 90% by weight of ethylene.
(b) Les terpolymères sont, avantageusement, choisis parmi les terpolymères statistiques ou séquencés, de préférence statistiques, d'éthylène, d'un monomère A et d'un monomère B. (b) The terpolymers are advantageously chosen from random or sequential terpolymers, preferably random, of ethylene, a monomer A and a monomer B.
Le monomère A est choisi parmi l'acétate de vinyle et les acrylates ou méthacrylates d'alkyle en Ci à C6. The A monomer is selected from vinyl acetate and alkyl acrylates or methacrylates to C 6.
Le monomère B est choisi parmi l'acrylate de glycidyle et le méthacrylate de glycidyle.  Monomer B is selected from glycidyl acrylate and glycidyl methacrylate.
Les terpolymères éthylène/monomère A/monomère B comprennent de 0,5% à 40% en masse, de préférence de 5% à 35% masse, plus préférentiellement de 10% à 30%) en masse de motifs issus du monomère A et, de 0,5% à 15% en masse, de préférence de 2,5% à 15% en masse de motifs issus du monomère B, le reste étant formé de motifs issus de l'éthylène.  The ethylene / monomer A / monomer B terpolymers comprise from 0.5% to 40% by weight, preferably from 5% to 35% by weight, more preferably from 10% to 30% by weight of units derived from monomer A, and from 0.5% to 15% by weight, preferably from 2.5% to 15% by weight of units derived from monomer B, the remainder being formed from units derived from ethylene.
(c) Les copolymères résultent du greffage d'un monomère B choisi parmi l'acrylate de glycidyle et le méthacrylate de glycidyle, sur un substrat polymère. Le substrat polymère consiste en un polymère choisi parmi les polyéthylènes, notamment les polyéthylènes basse densité, les polypropylènes, les copolymères statistiques ou séquencés, de préférence statistiques, d'éthylène et d'acétate de vinyle et les copolymère statistiques ou séquencés, de préférence statistiques, d'éthylène et d'acrylate ou méthacrylate d'alkyle en Ci à C6, comprenant de 40% à 99,7% en masse, de préférence de 50%> à 99% en masse d'éthylène. Lesdits copolymères greffés comprennent de 0,5%> à 15% en masse, de préférence de 2,5% à 15% en masse de motifs greffés issus du monomère B. Avantageusement, l'adjuvant polymère oléfmique est choisi parmi les terpolymères statistiques d'éthylène (b), d'un monomère A choisi parmi les acrylates ou méthacrylates d'alkyle en Ci à C6 et d'un monomère B choisi parmi l'acrylate de glycidyle et le méthacrylate de glycidyle, comprenant de 0,5% à 40% en masse, de préférence de 5% à 35% masse, plus préférentiellement de 10% à 30% en masse de motifs issus du monomère A et, de 0,5% à 15% en masse, de préférence de 2,5% à 15%) en masse de motifs issus du monomère B, le reste étant formé de motifs issus de l'éthylène. (c) The copolymers result from the grafting of a B monomer selected from glycidyl acrylate and glycidyl methacrylate onto a polymeric substrate. The substrate polymer consists of a polymer chosen from polyethylenes, in particular low-density polyethylenes, polypropylenes, statistical or block copolymers, preferably random copolymers of ethylene and vinyl acetate, and random or sequential copolymers, preferably random copolymers, of ethylene and alkyl acrylate or methacrylate to C 6, comprising from 40% to 99.7% by weight, preferably 50%> 99% by weight of ethylene. Said graft copolymers comprise from 0.5% to 15% by weight, preferably from 2.5% to 15% by weight of grafted units derived from monomer B. Advantageously, the olefinic polymer adjuvant is chosen from among the random terpolymers of ethylene (b), of a monomer a chosen from acrylates or methacrylates of alkyl to C 6 and a monomer B selected from glycidyl acrylate and glycidyl methacrylate, comprising 0.5% at 40% by weight, preferably from 5% to 35% by weight, more preferably from 10% to 30% by weight of units derived from monomer A and, from 0.5% to 15% by weight, preferably from 2%, 5% to 15%) by weight of units derived from monomer B, the remainder being formed from units derived from ethylene.
Selon un mode de réalisation de l'invention, la première composition, comprenant la base bitume, dont est composé le cœur des granules, comprend de 0,05%) à 15%) en masse, de préférence de 0,1% à 10% en masse, plus préférentiellement de 0,5% à 6% en masse de l'adjuvant polymère oléfmique, par rapport à la masse totale de la première composition.  According to one embodiment of the invention, the first composition, comprising the bitumen base, of which the core of the granules is composed, comprises from 0.05% to 15% by weight, preferably from 0.1% to 10% by weight. % by weight, more preferably from 0.5% to 6% by weight of the olefinic polymer adjuvant, relative to the total weight of the first composition.
Selon un mode de réalisation de l'invention, la première composition peut également comprendre d'autres additifs connus ou d'autres élastomères pour bitume connus tels que les copolymères SB (copolymère à blocs du styrène et du butadiène), SBS (copolymère à blocs styrène-butadiène-styrène), SIS (styrène-isoprène-styrène), SBS* (copolymère à blocs styrène-butadiène-styrène en étoile), SBR (styrène-b- butadiène-rubber), EPDM (éthylène propylène diène modifié). Ces élastomères peuvent en outre être réticulés selon tout procédé connu, par exemple avec du soufre. On peut également citer les élastomères réalisés à partir de monomères styrène et de monomères butadiène permettant une réticulation sans agent réticulant tels que décrits dans les documents WO2007/058994, WO2008/137394 et par la demanderesse dans la demande de brevet WOl 1/013073. Selon un mode de réalisation particulier préféré, la première composition comprend une combinaison de l'additif chimique de formule (II) et l'adjuvant polymère oléfïnique décrits ci-dessus. According to one embodiment of the invention, the first composition may also comprise other known additives or other known bitumen elastomers such as copolymers SB (block copolymer of styrene and butadiene), SBS (block copolymer). styrene-butadiene-styrene), SIS (styrene-isoprene-styrene), SBS * (star styrene-butadiene-styrene block copolymer), SBR (styrene-b-butadiene rubber), EPDM (modified ethylene propylene diene). These elastomers may also be crosslinked according to any known process, for example with sulfur. Mention may also be made of elastomers made from styrene monomers and butadiene monomers allowing crosslinking without a crosslinking agent as described in documents WO2007 / 058994, WO2008 / 137394 and by the applicant in the patent application WOl 1/013073. According to a particular preferred embodiment, the first composition comprises a combination of the chemical additive of formula (II) and the olefinic polymer adjuvant described above.
On préférera la combinaison dans laquelle l'additif chimique est de formule (II) où m=0, plus préférentiellement où m=0 et n=0.  We prefer the combination in which the chemical additive is of formula (II) where m = 0, more preferably where m = 0 and n = 0.
On préférera également la combinaison dans laquelle l'adjuvant polymère oléfïnique est choisi parmi les terpolymères (b) éthylène/monomère A/monomère B décrits ci-dessus.  The combination in which the olefinic polymer adjuvant is selected from the (b) ethylene / monomer A / monomer B terpolymers described above is also preferred.
Plus préférentiellement, le bitume routier comprend l'additif chimique de formule (II) où m=0, plus préférentiellement où m=0 et n=0 et l'adjuvant polymère oléfïnique choisi parmi les terpolymères (b) éthylène/monomère A/monomère B décrits ci-dessus.  More preferably, the road bitumen comprises the chemical additive of formula (II) where m = 0, more preferably where m = 0 and n = 0 and the olefinic polymer adjuvant chosen from terpolymers (b) ethylene / monomer A / monomer B described above.
Le composé anti-agglomérant : The anti-caking compound:
Le composé anti-agglomérant est d'origine minérale ou organique. Par « anti- agglomérant » ou « composé anti-agglomérant », on entend tout composé qui limite, réduit, inhibe, retarde, l'agglomération et/ou l'adhésion des granules entre eux lors de leur transport et/ou de leur stockage à température ambiante et qui assure leur fluidité lors de leur manipulation.  The anti-caking compound is of mineral or organic origin. By "anti-caking agent" or "anti-caking compound" is meant any compound which limits, reduces, inhibits, delays, the agglomeration and / or the adhesion of the granules together during their transport and / or their storage. at room temperature and which ensures their fluidity during handling.
Plus préférentiellement, le composé anti-agglomérant est choisi parmi : le talc ; les fines, également appelées "fïllers", généralement de diamètre inférieur à 125 μιη, telles que les fines silicieuses, à l'exception des fines calcaires ; le sable tel que le sable de fontainebleau ; le ciment ; le carbone ; les résidus de bois tels que la lignine, le lignosulfonate, les poudres d'aiguilles de conifères, les poudres de cônes de conifères, notamment de pin ; les cendres de balles de riz ; la poudre de verre ; les argiles telles que le kaolin, la bentonite, la vermiculite ; l'alumine telle que les hydrates d'alumine ; la silice ; les dérivés de silice tels que les fumées de silice, les fumées de silice fonctionnalisées, notamment les fumées de silice hydrophobe ou hydrophile, les silices pyrogénées, notamment les silices pyrogénées hydrophobes ou hydrophiles, les silicates, les hydroxydes de silicium et les oxydes de silicium ; la poudre de matière plastique ; la chaux ; le plâtre ; la poudrette de caoutchouc ; la poudre de polymères, tels que les copolymères styrène-butadiène (SB), les copolymères styrène-butadiène-styrène (SBS) et les mélanges de ces matériaux. Avantageusement, l'anti-agglomérant est choisi parmi le talc ; les fines généralement de diamètre inférieur à 125 μιη à l'exception des fines calcaires, telles que les fines siliceuses ; les résidus du bois tels que la lignine, la lignosulfonate, les poudres d'aiguilles de conifères, les poudres de cônes de conifères, notamment de pin; la poudre de verre ; le sable tel que le sable de fontainebleau ; les fumées de silice, notamment les fumées de silice hydrophobe ou hydrophile ; et leurs mélanges. More preferably, the anti-caking compound is chosen from: talc; fines, also called "fibers", generally of diameter less than 125 μιη, such as fine silicones, with the exception of fine limestones; sand such as fountain sand; cement ; carbon; wood residues such as lignin, lignosulphonate, conifer needle powders, conifer cone powders, especially pine powders; the ashes of rice balls; glass powder; clays such as kaolin, bentonite, vermiculite; alumina such as alumina hydrates; silica; silica derivatives such as silica fumes, functionalized silica fumes, in particular hydrophobic or hydrophilic silica fumes, pyrogenic silicas, especially hydrophobic or hydrophilic pyrogenic silicas, silicates, silicon hydroxides and silicon oxides ; plastic powder; lime; the plaster ; rubber crumb; polymer powder, such as styrene-butadiene copolymers (SB), styrene-butadiene-styrene copolymers (SBS) and mixtures of these materials. Advantageously, the anti-caking agent is chosen from talc; the fines generally of diameter less than 125 μιη with the exception of fine limestones, such as siliceous fines; wood residues such as lignin, lignosulphonate, conifer needle powders, conifer cone powders, especially pine powders; glass powder; sand such as fountain sand; silica fumes, especially hydrophobic or hydrophilic silica fumes; and their mixtures.
De préférence, le composé anti-agglomérant est choisi parmi les fumées de silice.  Preferably, the anti-caking compound is chosen from silica fumes.
Au sens de l'invention, les composés « fumée de silice », et « silice pyrogénée » ont la même définition chimique et sont enregistrés sous le même numéro CAS 112 945-52-5. Par conséquent, au sens de l'invention on peut employer ces composés indifféremment l'un de l'autre  For the purposes of the invention, the compounds "silica fume" and "fumed silica" have the same chemical definition and are registered under the same CAS number 112 945-52-5. Therefore, in the sense of the invention can be used these compounds indifferently from one another
Par « silice pyrogénée », on entend, soit une silice pyrogénée, soit un dérivé de silice pyrogénée.  By "fumed silica" is meant either a fumed silica or a fumed silica derivative.
Par « silice pyrogénée », on entend un composé obtenu par l'hydrolyse en phase vapeur de chlorosilanes tels que le tétrachlorure de silicium, dans une flamme d'oxygène et d'hydrogène. De tels procédés sont généralement désignés comme des procédés pyrogènes dont la réaction globale est : S1CI4 + H2 + 02→ Si02 + 4 HC1. Les silices pyrogénées se distinguent des autres dioxydes de silicium en ce qu'elles présentent une structure amorphe. De haute pureté (> 99,8 % en silice), elles présentent un faible caractère hydrophile (pas de microporosité). By "fumed silica" is meant a compound obtained by the vapor phase hydrolysis of chlorosilanes such as silicon tetrachloride, in a flame of oxygen and hydrogen. Such methods are generally referred to as pyrogenic processes whose overall reaction is: S1CI 4 + H 2 + O 2 → SiO 2 + 4 HCl. Pyrogenic silicas are distinguished from other silicon dioxides in that they have an amorphous structure. High purity (> 99.8% silica), they have a low hydrophilic character (no microporosity).
De préférence, le composé de silice pyrogénée est la silice pyrogénée.  Preferably, the fumed silica compound is fumed silica.
Selon un mode de réalisation de l'invention, le composé de silice pyrogénée présente une surface spécifique comprise entre 25 et 420 m2/g, préférentiellement entre 90 et 330 m2/g, plus préférentiellement entre 120 et 280 m2/g. According to one embodiment of the invention, the fumed silica compound has a specific surface area of between 25 and 420 m 2 / g, preferably between 90 and 330 m 2 / g, more preferably between 120 and 280 m 2 / g.
La surface spécifique de la silice pyrogénée définie en m2/g communément appelée « aire de surface » ou « SA » est mesurée selon la méthode de S. Brunauer, PH Emmet et I. Teller, J. Am. Chemical Society, 60: 309 (1938) (BET). The specific surface area of the fumed silica defined in m 2 / g commonly referred to as "surface area" or "SA" is measured according to the method of S. Brunauer, PH Emmet and I. Teller, J. Am. Chemical Society, 60: 309 (1938) (BET).
Selon un mode de réalisation de l'invention, le composé de silice pyrogénée présente une taille moyenne de particules comprise entre 5 et 50 nm.  According to one embodiment of the invention, the fumed silica compound has an average particle size of between 5 and 50 nm.
Selon un mode de réalisation de l'invention, le composé de silice pyrogénée présente un pH compris entre 3 et 10 lorsqu'il est en phase aqueuse. Selon un mode de réalisation de l'invention, le composé de silice pyrogénée présente une teneur de carbone comprise entre 0,1 et 10% en poids par rapport au poids total du composé de silice pyrogénée. According to one embodiment of the invention, the fumed silica compound has a pH of between 3 and 10 when in the aqueous phase. According to one embodiment of the invention, the fumed silica compound has a carbon content of between 0.1 and 10% by weight relative to the total weight of the fumed silica compound.
Selon un mode de réalisation de l'invention, le composé de silice pyrogénée est choisi parmi un composé de silice pyrogénée hydrophile, un composé de silice pyrogénée hydrophobe et leurs mélanges.  According to one embodiment of the invention, the fumed silica compound is selected from a hydrophilic fumed silica compound, a hydrophobic fumed silica compound and mixtures thereof.
De préférence, le composé de silice pyrogénée est un composé de silice pyrogénée hydrophile.  Preferably, the fumed silica compound is a hydrophilic fumed silica compound.
Par « hydrophile », on entend un composé qui est miscible avec l'eau en toutes proportions.  By "hydrophilic" is meant a compound that is miscible with water in all proportions.
Le composé de silice pyrogénée, ou dérivé de silice pyrogénée, utilisé au sens de l'invention peut être chimiquement modifié.  The fumed silica compound, or fumed silica derivative, used within the meaning of the invention may be chemically modified.
Différents types de composés de silice pyrogénée sont décrits dans les demandes de brevets suivants et peuvent être utilisés dans la présente invention :  Various types of fumed silica compounds are described in the following patent applications and may be used in the present invention:
- des silices pyrogénées silanisées, comme décrit dans WO 2004/020532, ou dans WO 2007/128636,  silanized fumed silicas, as described in WO 2004/020532, or in WO 2007/128636,
- des silices pyrogénées hydrophiles, comme décrit dans WO 2009/071467, WO 2011/000133 déposés au nom de Degussa AG ou Degussa Gmbh,  hydrophilic pyrogenic silicas, as described in WO 2009/071467, WO 2011/000133 filed in the name of Degussa AG or Degussa Gmbh,
- des fumées de silice rendues hydrophobes par un traitement au moyen de polysiloxanes comme décrit dans WO 2008/141932, ou par silanisation comme décrit dans WO 2008/141930,  silica fumes made hydrophobic by treatment with polysiloxanes as described in WO 2008/141932, or by silanization as described in WO 2008/141930,
- des silices dopées par de l'oxyde de potassium comme décrit dans WO 2008/043635, WO 2008/022836,  silicas doped with potassium oxide as described in WO 2008/043635, WO 2008/022836,
- des silices sous forme d'agrégats de particules primaires comme décrit dans WO 2009/015969 déposé au nom de Evonik Degussa Gmbh ou dans WO silicas in the form of aggregates of primary particles as described in WO 2009/015969 filed in the name of Evonik Degussa Gmbh or in WO
2010/028261 déposé au nom de Cabot Corporation. 2010/028261 filed in the name of Cabot Corporation.
Le composé de silice pyrogénée peut être mis en œuvre seul ou sous forme d'un mélange au sein d'une composition de revêtement.  The fumed silica compound can be used alone or as a mixture in a coating composition.
Qu'il soit mis en œuvre seul ou en mélange dans une composition, le composé de silice pyrogénée peut être mis en œuvre dans le procédé selon l'invention sous la forme d'une poudre ou en dispersion dans un solvant qui s'évapore après application.  Whether it is used alone or as a mixture in a composition, the fumed silica compound can be used in the process according to the invention in the form of a powder or in dispersion in a solvent which evaporates after application.
De préférence, lorsque la composition comprend au moins un composé de silice pyrogénée et au moins un solvant, la composition comprend de 5 à 70%> en poids de composé de silice pyrogénée par rapport au poids total de la composition, plus préférentiellement de 20 à 40% en poids. Preferably, when the composition comprises at least one fumed silica compound and at least one solvent, the composition comprises from 5 to 70% by weight of fumed silica compound relative to the total weight of the composition, more preferably from 20 to 40% by weight.
De préférence, le solvant est un solvant organique ou de l'eau. Par solvant organique, on entend tout solvant non miscible avec un bitume, tel qu'un alcool, par exemple l'éthanol.  Preferably, the solvent is an organic solvent or water. By organic solvent is meant any solvent immiscible with a bitumen, such as an alcohol, for example ethanol.
Les composés de silice pyrogénée utilisés dans l'invention sont commercialement disponibles et par exemple peuvent être vendus par Evonik Degussa sous la marque AEROSIL®, comme par exemple l'AEROSIL®200, par Cabot Corporation sous les marques CAB-O-SIL® et CAB-O-SPERSE® ou encore par Wacker Chemie AG sous la marque HDK®. The compounds of fumed silica used in the invention are commercially available and for example may be sold by Evonik Degussa under the tradename Aerosil ® such as Aerosil ® 200 the, by Cabot Corporation under the Cab-O-Sil ® and CAB-O-SPERSE ® or by Wacker Chemie AG under the brand name HDK ® .
Selon un mode de réalisation de l'invention, la masse du composé de silice pyrogénée recouvrant au moins une partie de la surface des granules est comprise entre 0,2% et 10%> en masse, de préférence entre 0,5%> et 8% en masse, plus préférentiellement entre 0,5% et 5% par rapport à la masse totale de la première composition.  According to one embodiment of the invention, the mass of the fumed silica compound covering at least a portion of the surface of the granules is between 0.2% and 10% by weight, preferably between 0.5% and 8% by weight, more preferably between 0.5% and 5% relative to the total mass of the first composition.
Les granules de la première composition sont recouverts du composé de silice pyrogénée selon tout procédé connu, par exemple selon le procédé décrit dans le document US 3 026 568.  The granules of the first composition are covered with the fumed silica compound according to any known method, for example according to the process described in US Pat. No. 3,026,568.
Selon un mode de réalisation de l'invention, le cœur des granules comprend en outre au moins un composé de silice pyrogénée tel que défini ci-dessus.  According to one embodiment of the invention, the core of the granules further comprises at least one fumed silica compound as defined above.
De préférence, le cœur des granules de la première composition comprend en outre entre 0,5%> et 20%> en masse, de préférence entre 2% et 20%> en masse, plus préférentiellement entre 4% et 15% en masse du composé de silice pyrogénée par rapport à la masse totale de la première composition.  Preferably, the core of the granules of the first composition further comprises between 0.5% and 20% by weight, preferably between 2% and 20% by weight, more preferably between 4% and 15% by weight of the composition. fumed silica compound with respect to the total mass of the first composition.
Composé viscosifiant : Viscosifying compound:
Les termes « viscosifiant » et « composé viscosifiant » sont utilisés au sens de l'invention, de manière équivalente et indépendamment l'un de l'autre. Par « viscosifiant » ou « composé viscosifiant », on entend un composé qui a la propriété de diminuer la fluidité d'un liquide ou d'une composition et donc d'en augmenter la viscosité.  The terms "viscosifier" and "viscosifying compound" are used in the sense of the invention, in an equivalent manner and independently of one another. By "viscosifier" or "viscosifying compound" is meant a compound which has the property of decreasing the fluidity of a liquid or a composition and thus increasing its viscosity.
Le viscosifiant au sens de l'invention est un matériau qui présente une viscosité dynamique supérieure ou égale à 50 mPa.s"1, de préférence de 50 mPa.s"1 à 550 mPa.s" plus préférentiellement de 80 mPa.s"1 à 450 mPa.s"1, la viscosité étant une viscosité Brookfïeld mesurée à 65°C. La viscosité d'un viscosifiant selon l'invention est mesurée à 65°C au moyen d'un viscosimètre Brookfïeld CAP 2000+ et à une vitesse de rotation de 750 tr/min. La lecture de la mesure est réalisée après 30 secondes pour chaque température. The viscosifier within the meaning of the invention is a material which has a dynamic viscosity greater than or equal to 50 mPa · s "1, preferably 50 mPa.s" 1-550 mPa.s " more preferably from 80 mPa.s "1 to 450 mPa.s " 1 , the viscosity being a Brookfield viscosity measured at 65 ° C. The viscosity of a viscosifier according to the invention is measured at 65 ° C. by means of a Brookfield CAP 2000+ viscometer and at a rotation speed of 750 rpm. The measurement is read after 30 seconds for each temperature.
De préférence, le viscosifiant est choisi parmi :  Preferably, the viscosifier is chosen from:
- les composés gélifiants de préférence d'origine végétale ou animale, tels que : la gélatine, l'agar-agar, les alginates, les dérivés de cellulose, les amidons, les amidons modifiés, ou les gommes gellanes ;  gelling compounds, preferably of vegetable or animal origin, such as: gelatin, agar-agar, alginates, cellulose derivatives, starches, modified starches, or gellan gums;
- les polyéthylène glycols (PEG) tels que les PEG ayant un poids moléculaire compris entre 800 g.mol"1 et 8000 g.mol"1, comme par exemple un PEG ayant un poids moléculaire de 800 g.mol"1 (PEG-800), un PEG ayant un poids moléculaire de 1000 g.mol"1 (PEG-1000), un PEG ayant un poids moléculaire de 1500 g.mol"1 (PEG- 1500), un PEG ayant un poids moléculaire de 4000 g.mol"1 (PEG-4000) ou un PEG ayant un poids moléculaire de 6000 g.mol"1 (PEG-6000); polyethylene glycols (PEG) such as PEGs having a molecular weight of between 800 gmol -1 and 8000 g mol -1 , for example a PEG having a molecular weight of 800 gmol -1 (PEG- 1); 800), a PEG having a molecular weight of 1000 gmol -1 (PEG-1000), a PEG having a molecular weight of 1500 g mol -1 (PEG-1500), a PEG having a molecular weight of 4000 g .mol "1 (PEG-4000) or PEG having a molecular weight of 6000 gmol -1 (PEG-6000);
- les mélanges de tels composés.  mixtures of such compounds.
Avantageusement, le viscosifiant est choisi parmi :  Advantageously, the viscosifier is chosen from:
- les composés gélifiants de préférence d'origine végétale ou animale, tels que : la gélatine, l'agar-agar, les alginates, les dérivés de cellulose ou les gommes gellanes ;  gelling compounds, preferably of vegetable or animal origin, such as: gelatin, agar-agar, alginates, cellulose derivatives or gellan gums;
- les polyéthylène glycols (PEG) tels que les PEG ayant un poids moléculaire compris entre 800 g.mol"1 et 8000 g.mol"1, comme par exemple un PEG ayant un poids moléculaire de 800 g.mol"1 (PEG-800), un PEG ayant un poids moléculaire de 1000 g.mol"1 (PEG-1000), un PEG ayant un poids moléculaire de 1500 g.mol"1 (PEG- 1500), un PEG ayant un poids moléculaire de 4000 g.mol"1 (PEG-4000) ou un PEG ayant un poids moléculaire de 6000 g.mol"1 (PEG-6000); polyethylene glycols (PEG) such as PEGs having a molecular weight of between 800 gmol -1 and 8000 g mol -1 , for example a PEG having a molecular weight of 800 gmol -1 (PEG- 1); 800), a PEG having a molecular weight of 1000 gmol -1 (PEG-1000), a PEG having a molecular weight of 1500 g mol -1 (PEG-1500), a PEG having a molecular weight of 4000 g .mol "1 (PEG-4000) or PEG having a molecular weight of 6000 gmol -1 (PEG-6000);
- les mélanges de tels composés.  mixtures of such compounds.
La couche de revêtement : The coating layer:
Selon un premier mode de réalisation de l'invention, la couche de revêtement est obtenue par application d'une composition (seconde composition) comprenant au moins un composé anti-agglomérant sur tout ou partie de la surface du cœur des granules, notamment de bitume solide. De préférence, selon ce mode de réalisation, la couche de revêtement consiste essentiellement en un ou plusieurs composés anti-agglomérants. According to a first embodiment of the invention, the coating layer is obtained by applying a composition (second composition) comprising at least one anti-caking compound on all or part of the core surface of the granules, in particular bitumen. solid. Preferably, according to this embodiment, the coating layer consists essentially of one or more anti-caking compounds.
De préférence, selon ce mode de réalisation, la masse du composé anti- agglomérant recouvrant au moins une partie de la surface des granules est de 0,2% à 20% en masse, de préférence de 0,5%> à 20%> en masse, de préférence de 2% à 20%> en masse, plus préférentiellement de 4% à 15% en masse par rapport à la masse totale des cœurs de granules, notamment de base bitume des granules.  Preferably, according to this embodiment, the mass of the anti-caking compound covering at least a portion of the surface of the granules is 0.2% to 20% by weight, preferably 0.5% to 20%> in bulk, preferably from 2% to 20% by weight, more preferably from 4% to 15% by weight relative to the total mass of the granule cores, in particular of the bitumen base of the granules.
Selon ce mode de réalisation, et lorsque que le composé anti-agglomérant est choisi parmi les composés de silice pyrogénée, la masse du composé de silice pyrogénée recouvrant au moins une partie de la surface des granules est comprise entre 0,2%> et 10%> en masse, de préférence entre 0,5%> et 8% en masse, plus préférentiellement entre 0,5% et 5% par rapport à la masse totale de la première composition. Selon un second mode de réalisation de l'invention, la couche de revêtement est obtenue par application d'une composition (seconde composition) comprenant au moins un composé viscosifïant et au moins un composé anti-agglomérant sur tout ou partie de la surface du cœur des granules, notamment de bitume solide.  According to this embodiment, and when the anti-caking compound is chosen from pyrogenic silica compounds, the mass of the fumed silica compound covering at least a portion of the surface of the granules is between 0.2% and 10%. %> by weight, preferably between 0.5%> and 8% by weight, more preferably between 0.5% and 5% relative to the total weight of the first composition. According to a second embodiment of the invention, the coating layer is obtained by applying a composition (second composition) comprising at least one viscosifying compound and at least one anti-caking compound on all or part of the surface of the core. granules, in particular solid bitumen.
De préférence, la couche de revêtement, formée à partir de la seconde composition, est solide à température ambiante, y compris à température ambiante élevée.  Preferably, the coating layer, formed from the second composition, is solid at ambient temperature, including at elevated ambient temperature.
De préférence, la seconde composition, comprenant au moins un composé viscosifïant et au moins un composé anti-agglomérant présente une viscosité supérieure ou égale à 200 mPa.s"1, de préférence comprise entre 200 mPa.s"1 et 700 mPa.s"1, la viscosité étant une viscosité Brookfïeld. Preferably, the second composition, comprising at least one viscosifying compound and at least one anti-caking compound has a viscosity greater than or equal to 200 mPa.s -1 , preferably between 200 mPa.s -1 and 700 mPa.s. 1 , the viscosity being Brookfield viscosity.
Préférentiellement, la seconde composition comprend au moins 10% en masse d'au moins un composé viscosifïant par rapport à la masse totale de la seconde composition, de préférence de 10 à 90 % en masse, plus préférentiellement de 10 à 85%o en masse.  Preferably, the second composition comprises at least 10% by weight of at least one viscosifying compound relative to the total mass of the second composition, preferably from 10 to 90% by weight, more preferably from 10 to 85% by weight. .
Avantageusement, lorsque le vicosifïant est un gélifiant, comme par exemple de la gélatine, la seconde composition comprend de 10 à 90 % en masse de composé viscosifïant par rapport à la masse totale de la seconde composition, de préférence de 15 à 85%), encore mieux de 15 à 60%. Avantageusement, lorsque le vicosifïant est un gélifiant, comme par exemple de la gélatine, la seconde composition comprend de 10 à 90 % en masse de composé anti- agglomérant par rapport à la masse totale de la seconde composition, de préférence de 15 à 85%, encore mieux de 40 à 85%. Advantageously, when the vicosifier is a gelling agent, for example gelatin, the second composition comprises from 10 to 90% by weight of viscosifying compound relative to the total weight of the second composition, preferably from 15 to 85%), even better from 15 to 60%. Advantageously, when the vicosifier is a gelling agent, such as, for example, gelatin, the second composition comprises from 10 to 90% by weight of anti-caking compound relative to the total weight of the second composition, preferably from 15 to 85%. even better from 40 to 85%.
Avantageusement, lorsque le vicosifïant est un PEG, comme par exemple un Advantageously, when the vicosifant is a PEG, such as for example
PEG ayant un poids moléculaire compris entre 800 g.mol"1 et 8000 g.mol"1, la seconde composition comprend de 10 à 90 % en masse de composé viscosifîant par rapport à la masse totale de seconde composition, de préférence de 40 à 90%, encore mieux de 60 à 90%. PEG having a molecular weight of between 800 gmol -1 and 8000 g mol -1 , the second composition comprises from 10 to 90% by weight of viscosifying compound relative to the total mass of the second composition, preferably from 40 to 90%, even better 60 to 90%.
Avantageusement, lorsque le vicosifïant est un PEG, comme par exemple un Advantageously, when the vicosifant is a PEG, such as for example
PEG ayant un poids moléculaire compris entre 800 g.mol"1 et 8000 g.mol"1, la seconde composition comprend de 10 à 90 % en masse de composé anti-agglomérant par rapport à la masse totale de la seconde composition, de préférence de 10 à 60%>, encore mieux de 10 à 40%. PEG having a molecular weight of between 800 gmol -1 and 8000 g mol -1 , the second composition comprises from 10 to 90% by weight of anti-caking compound relative to the total mass of the second composition, preferably from 10 to 60%, more preferably from 10 to 40%.
Préférentiellement, la seconde composition comprend au moins 10% en masse d'un composé anti-agglomérant par rapport à la masse totale de la seconde composition, de préférence de 10 à 90%> en masse, encore plus préférentiellement de 15 à 90 % en masse.  Preferably, the second composition comprises at least 10% by weight of an anti-caking compound relative to the total mass of the second composition, preferably from 10 to 90% by weight, more preferably from 15 to 90% by weight. mass.
De préférence, selon ce mode de réalisation, la couche de revêtement représente au moins 5% en masse par rapport à la masse totale du granule, de préférence de 10 à 60%) en masse, plus préférentiellement de 10 à 50%.  Preferably, according to this embodiment, the coating layer represents at least 5% by weight relative to the total mass of the granule, preferably from 10 to 60% by weight, more preferably from 10 to 50%.
Outre le composé viscosifîant et le composé anti-agglomérant, la seconde composition formant la couche de revêtement peut éventuellement comprendre un ou plusieurs composés choisis parmi : les additifs chimiques, les polymères, ...  In addition to the viscosifying compound and the anti-caking compound, the second composition forming the coating layer may optionally comprise one or more compounds chosen from: chemical additives, polymers, etc.
Avantageusement, le composé viscosifîant et le composé anti-agglomérant représentent au moins 90% en masse par rapport à la masse totale de la seconde composition formant la couche de revêtement, encore mieux au moins 95% en masse et avantageusement au moins 98% en masse.  Advantageously, the viscosifying compound and the anti-caking compound represent at least 90% by weight relative to the total mass of the second composition forming the coating layer, more preferably at least 95% by weight and advantageously at least 98% by weight. .
Selon un mode de réalisation préféré de cette seconde variante, la seconde composition est essentiellement constituée du composé viscosifîant et du composé anti-agglomérant. Utilisations des granules de bitume solide According to a preferred embodiment of this second variant, the second composition essentially consists of the viscosifying compound and the anti-caking compound. Uses of solid bitumen granules
Les granules de matériau, de préférence de bitume, solide obtenus par le procédé de l'invention peuvent être utilisés comme liant routier.  The granules of material, preferably bitumen, solid obtained by the process of the invention can be used as road binder.
Le liant routier peut être employé pour fabriquer des enrobés, en association avec des granulats selon tout procédé connu.  The road binder can be used to manufacture mixes, in combination with aggregates according to any known method.
De préférence, les granules de matériau solide à température ambiante selon l'invention sont utilisés pour la fabrication d'enrobés.  Preferably, the granules of solid material at room temperature according to the invention are used for the manufacture of asphalt.
Les enrobés bitumineux sont utilisés comme matériaux pour la construction et l'entretien des corps de chaussée et de leur revêtement, ainsi que pour la réalisation de tous travaux de voiries. On peut citer par exemple les enduits superficiels, les enrobés à chaud, les enrobés à froid, les enrobés coulés à froid, les graves émulsions, les couches de bases, de liaison, d'accrochage et de roulement, et d'autres associations d'un liant bitumineux et du granulat routier possédant des propriétés particulières, telles que les couches anti-orniérantes, les enrobés drainants, ou les asphaltes (mélange entre un liant bitumineux et des granulats du type du sable).  Bituminous mixes are used as materials for the construction and maintenance of pavement bodies and their pavement, as well as for the realization of all road works. For example, superficial coatings, hot mixes, cold mixes, cold mixes, low emulsions, base layers, binding, hooking and rolling, and other combinations of a bituminous binder and road aggregate having particular properties, such as anti-rutting layers, draining asphalts, or asphalts (mixture between an asphalt binder and sand-like aggregates).
Les granules de matériau solide, notamment de bitume solide obtenus par le procédé de l'invention peuvent être mis en œuvre dans un procédé de fabrication d'enrobés comprenant au moins un liant routier et des granulats, le liant routier étant choisi parmi les granules de matériau solide, notamment de bitumes selon l'invention, ce procédé comprenant au moins les étapes de :  The granules of solid material, in particular solid bitumen obtained by the method of the invention can be implemented in a process for the manufacture of mixes comprising at least one road binder and aggregates, the road binder being chosen from among the granules of solid material, in particular bitumen according to the invention, this process comprising at least the steps of:
- chauffage des granulats à une température allant de 100°C à 180°C, de préférence de 120°C à 160°C,  heating the aggregates at a temperature ranging from 100 ° C. to 180 ° C., preferably from 120 ° C. to 160 ° C.,
- mélange des granulats avec le liant routier dans une cuve telle qu'un malaxeur ou un tambour malaxeur,  mixing the aggregates with the road binder in a tank such as a kneader or a kneading drum,
- obtention d'enrobés.  - Obtaining mixes.
Le procédé de l'invention présente l'avantage de pouvoir être mis en œuvre sans étape préalable de chauffage des granules de matériau solide, notamment de bitume solide.  The method of the invention has the advantage of being able to be implemented without prior step of heating the granules of solid material, in particular solid bitumen.
Le procédé de fabrication d'enrobés ne requiert pas d'étape de chauffage des granules de matériau solide, notamment de bitume solide avant mélange avec les granulats car au contact des granulats chauds, le matériau solide, notamment le bitume solide à température ambiante fond. Le matériau solide, notamment le bitume solide à température ambiante obtenu par le procédé selon l'invention tel que décrit ci-dessus présente l'avantage de pouvoir être ajouté directement aux granulats chauds, sans avoir à être fondu préalablement au mélange avec les granulats chauds. The asphalt manufacturing process does not require a step of heating the granules of solid material, in particular solid bitumen before mixing with the aggregates because, in contact with the hot aggregates, the solid material, especially solid bitumen at ambient temperature, melts. The solid material, in particular the ambient-temperature solid bitumen obtained by the process according to the invention as described above, has the advantage of being able to be added directly to the hot aggregates, without having to be melted before mixing with the hot aggregates. .
De préférence, l'étape de mélange des granulats et du liant routier est réalisée sous agitation, puis l'agitation est maintenue pendant au plus 5 minutes, de préférence au plus 1 minute pour permettre l'obtention d'un mélange homogène.  Preferably, the step of mixing the aggregates and road binder is carried out with stirring, then the stirring is maintained for at most 5 minutes, preferably at most 1 minute to allow to obtain a homogeneous mixture.
Le matériau solide, notamment le bitume solide, sous forme de granules obtenu selon le procédé de la présente invention est remarquable en ce qu'il permet le transport et/ou le stockage de matériau solide, notamment de bitume routier, à température ambiante dans des conditions optimales, en particulier sans qu'il y ait agglomération et/ou adhésion du matériau solide, notamment de bitume solide, lors de son transport et/ou son stockage, même lorsque la température ambiante est élevée. Par ailleurs, la couche de revêtement des granules casse sous l'effet du contact avec les granulats chauds et du cisaillement et il libère la première composition, notamment la base bitume. Enfin, la présence de la couche de revêtement dans le mélange de liant routier et de granulats ne dégrade pas les propriétés dudit bitume routier pour une application routière, comparativement à une base bitume non enrobée. Procédé de transport et/ou de stockage et/ou de manipulation de matériau solide utilisable comme liant routier ou comme liant de revêtement  The solid material, in particular solid bitumen, in the form of granules obtained according to the method of the present invention is remarkable in that it allows the transport and / or storage of solid material, in particular road bitumen, at ambient temperature in optimum conditions, in particular without there being agglomeration and / or adhesion of the solid material, especially solid bitumen, during its transport and / or its storage, even when the ambient temperature is high. Furthermore, the coating layer of the granules breaks under the effect of contact with hot aggregates and shear and releases the first composition, especially the bitumen base. Finally, the presence of the coating layer in the road binder mixture and aggregates does not degrade the properties of said road bitumen for road application, compared to an uncoated bitumen base. Method of transporting and / or storing and / or handling solid material useful as a road binder or as a coating binder
Les granules obtenus par le procédé de l'invention peuvent être transportés et/ou stockés et/ou de manipulés sous forme de granules de matériau solide, notamment de bitume, solides à température ambiante.  The granules obtained by the process of the invention can be transported and / or stored and / or manipulated in the form of granules of solid material, in particular bitumen, solid at ambient temperature.
Le matériau solide, notamment le bitume routier, peut être transporté et/ou stocké à une température ambiante élevée pendant une durée supérieure ou égale à 2 mois, préférence à 3 mois.  The solid material, especially road bitumen, can be transported and / or stored at a high ambient temperature for a period greater than or equal to 2 months, preferably 3 months.
De préférence, la température ambiante élevée est de 20°C à 90°C, de préférence de 20°C à 80°C, plus préférentiellement de 40°C à 80°C, encore plus préférentiellement de 40°C à 60°C.  Preferably, the high ambient temperature is from 20 ° C to 90 ° C, preferably from 20 ° C to 80 ° C, more preferably from 40 ° C to 80 ° C, still more preferably from 40 ° C to 60 ° C .
Les granules de matériau solide, notamment de bitume, obtenus par le procédé selon l'invention présentent l'avantage de conserver leur forme divisée, et donc de pouvoir être manipulés, après un stockage et/ou un transport à une température ambiante élevée. Ils présentent en particulier la capacité de s'écouler sous leur propre poids sans fluer, ce qui permet leur stockage dans un conditionnement en sacs, en fûts ou en containers de toutes formes et de tous volumes puis leur transvasement depuis ce conditionnement vers un équipement, comme un équipement de chantier (cuve, mélangeur etc .). The granules of solid material, in particular bitumen, obtained by the process according to the invention have the advantage of keeping their divided form, and therefore of being able to be handled, after storage and / or transport at a temperature. high ambient. They have in particular the ability to flow under their own weight without flowing, which allows their storage in a packaging bags, drums or containers of all shapes and volumes and their transfer from this packaging to equipment, as a construction equipment (tank, mixer etc).
Les granules de matériau solide, notamment de bitume, sont, de préférence, transportés et/ou du stockés en vrac dans des sacs de 1 kg à 100 kg ou de 500 kg à 1000 kg couramment appelés dans le domaine des bitumes routiers des « Big Bag », lesdits sacs étant de préférence en matériau thermo fusible. Ils peuvent également être transportés et/ou stockés en vrac dans des cartons de 5 kg à 30 kg ou dans des fûts de 100 kg à 200 kg.  The granules of solid material, especially bitumen, are preferably transported and / or stored in bulk in bags of 1 kg to 100 kg or 500 kg to 1000 kg commonly known in the field of road bitumens of "Big Bag ", said bags being preferably of heat-fusible material. They may also be transported and / or stored in bulk in cartons of 5 kg to 30 kg or in drums of 100 kg to 200 kg.
Les différents modes de réalisation, variantes, les préférences et les avantages décrits ci-dessus pour chacun des objets de l'invention s'appliquent à tous les objets de l'invention et peuvent être pris séparément ou en combinaison.  The various embodiments, variants, preferences and advantages described above for each of the objects of the invention apply to all the objects of the invention and can be taken separately or in combination.
L'invention est illustrée par les exemples suivants donnés à titre non limitatif.  The invention is illustrated by the following examples given without limitation.
Dispositif Device
L'invention concerne également un dispositif pour la mise en œuvre du procédé décrit ci-dessus. Ce dispositif décrit sur les figures 1 à 3 est un appareil pour l'extrusion sous forme de pastilles, également nommée « pastillation », sur une bande de roulement, d'une masse fluide de matériau solide à température ambiante, utilisable comme liant routier ou comme liant d'étanchéité, tel qu'un bitume routier, un brai, une solution mère pour composition bitume/polymère, un liant clair. Un tel dispositif constitue un perfectionnement du dispositif décrit dans US-4,279,579. Ce dispositif 1 comprend : un premier tambour cylindrique 4A disposé au-dessus de la bande de roulement 6 et capable d'une rotation autour d'un axe longitudinal, ledit premier tambour 4A comprenant une pluralité de premiers passages 5A à travers la périphérie du tambour 4A, un second tambour cylindrique 4B coaxial du premier tambour 4A, comportant des moyens 17 permettant d'admettre longitudinalement dans ledit second tambour 4B la masse à extruder et comportant sur une partie de sa paroi une pluralité de seconds passages 5B dirigés vers la bande de roulement 6 et alignés radialement avec lesdits premiers passages 5 A, ladite partie de paroi 19 étant disposée de façon adjacente audit premier tambour 4 A, ledit premier tambour 4 A étant monté pour permettre sa rotation continue sur 360 ° autour de l'axe longitudinal par rapport audit deuxième tambour 4B de telle sorte que la rotation relative entre lesdits tambours 4A et 4B produit de façon séquentielle un défaut d'alignement et un alignement des premiers passages 5A et seconds passages 5B pour permettre à la masse fluide de se déplacer radialement vers l'extérieur à travers les passages alignés, 5A, 5B et sur la bande de roulement 6A, ce dispositif comprenant en outre, comme illustré sur la figure 1 : The invention also relates to a device for implementing the method described above. This device described in FIGS. 1 to 3 is an apparatus for the extrusion in the form of pellets, also called "pastillation", on a tread, of a fluid mass of solid material at ambient temperature, which can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a stock solution for bitumen / polymer composition, a clear binder. Such a device is an improvement of the device described in US-4,279,579. This device 1 comprises: a first cylindrical drum 4A disposed above the tread 6 and capable of rotation about a longitudinal axis, said first drum 4A comprising a plurality of first passages 5A through the periphery of the drum 4A, a second coaxial cylindrical drum 4B of the first drum 4A, comprising means 17 for admitting longitudinally into said second drum 4B the mass to be extruded and having on a part of its wall a plurality of second passages 5B directed towards the strip of bearing 6 and aligned radially with said first passages 5A, said wall portion 19 being disposed adjacent said first drum 4A, said first drum 4A being mounted for allow its continuous rotation 360 ° about the longitudinal axis relative to said second drum 4B so that the relative rotation between said drums 4A and 4B sequentially produces a misalignment and alignment of the first passages 5A and the second passages 5B for allowing the fluid mass to move radially outwardly through the aligned passages 5A, 5B and on the tread 6A, which device further comprises, as illustrated in FIG.
- un réservoir 11 équipé de moyens de chauffage (non représentés), et de moyens d'agitation 13, permettant de porter le contenant du réservoir 11, à l'état fluide,  a tank 11 equipped with heating means (not shown), and stirring means 13, for carrying the container of the tank 11, in the fluid state,
- un canal, ou plusieurs canaux, d'injection 3 permettant le transfert de la composition de bitume 2 fluide à l'intérieur du second tambour 4B,  a channel, or several channels, of injection 3 allowing the transfer of the fluid bitumen composition 2 inside the second drum 4B,
- un réservoir 14 dans lequel on peut introduire une composition d'additifs 15, le réservoir 14 étant relié au canal d'injection 3 au travers d'un injecteur 16 et permettant une injection de la composition d'additifs 15 dans la composition de bitume 2 au niveau du canal 3, situé en aval du réservoir 11 et en amont du double tambour 4.  a reservoir 14 in which an additive composition 15 can be introduced, the reservoir 14 being connected to the injection channel 3 through an injector 16 and allowing an injection of the additive composition 15 into the bitumen composition 2 at the channel 3, located downstream of the tank 11 and upstream of the double drum 4.
Comme décrit dans US-4,279,579, de préférence, ce dispositif comprend en outre une spatule pour enlever la masse en excès du périmètre dudit premier tambour 4A, ladite spatule étant dirigé vers ledit premier tambour 4A généralement dans le sens de rotation de celui-ci, ladite spatule étant fermement pressée contre le périmètre dudit premier tambour 4A dans la région desdits premiers passages 5A de façon à gratter excès de masse dans lesdits premiers passages 5A. As described in US-4,279,579, preferably, this device further comprises a spatula for removing excess mass from the perimeter of said first drum 4A, said spatula being directed towards said first drum 4A generally in the direction of rotation thereof, said spatula being firmly pressed against the perimeter of said first drum 4A in the region of said first passages 5A so as to scratch excess mass in said first passages 5A.
Comme décrit dans US-4,279,579, de préférence, les premiers passages 4A décalés sur la circonférence sont reliés entre eux par des rainures disposées le long de la périphérie du premier tambour 4A.  As described in US Pat. No. 4,279,579, preferably, the first circumferentially-shifted first passages 4A are interconnected by grooves disposed along the periphery of the first drum 4A.
Comme décrit dans US-4,279,579, de préférence, chaque rainure se prolonge dans une direction de spirale, chaque rainure reliant les ouvertures qui se trouvent dans des plans parallèles qui sont disposées perpendiculairement à l'axe du tambour et qui se trouvent sur différentes lignes imaginaires longitudinales s'étendant le long de la périphérie dudit premier tambour.  As described in US Pat. No. 4,279,579, each groove preferably extends in a spiral direction, each groove connecting the openings in parallel planes which are arranged perpendicular to the axis of the drum and which are on different imaginary lines. longitudinally extending along the periphery of said first drum.
L'invention a encore pour objet un dispositif pour l'extrusion de gouttes d'une masse fluide sur une bande de roulement 6, ledit dispositif comprenant: un premier tambour cylindrique 4A comprenant une pluralité de premiers passages 5A, un second tambour cylindrique 4B disposé à l'intérieur dudit premier tambour 4A et comprenant une pluralité de seconds passages 5B, des moyens 17 pour admettre un matériau fluide dans ledit second tambour 4B, des moyens pour produire une rotation relative entre lesdits tambours 4A, 4B, pour aligner périodiquement lesdits premier passages 4A et second passages 4B, pour déposer des gouttes 7 de matériau fluide à travers les passages 4A, 4B, et sur le convoyeur 6, lesdits premier et second tambours 4A, 4B étant montés pour se séparer radialement l'un de l'autre au cours de ladite la rotation relative de manière à former un interstice entre lesdits premier et second tambours 4A, 4B sous pression négative à un emplacement opposé à l'emplacement où les passages sont alignés régulièrement, de façon à aspirer dans la masse de matériau en excès dans lesdits passages 5A dudit premier tambour 4A, ce dispositif comprenant en outre, comme illustré sur la figure 1 : The invention further relates to a device for the extrusion of drops of a fluid mass on a tread 6, said device comprising: a first cylindrical drum 4A comprising a plurality of first passages 5A, a second cylindrical drum 4B disposed within said first drum 4A and comprising a plurality of second passages 5B, means 17 for admitting a fluid material into said second drum 4B, means for producing a relative rotation between said drums 4A, 4B, for periodically aligning said first passages 4A and second passages 4B, for depositing drops of fluid material through passages 4A, 4B, and on conveyor 6, said first and second drums 4A, 4B being mounted to separate radially from one another; the other during said relative rotation so as to form a gap between said first and second drums 4A, 4B under negative pressure at a location opposite the location where the passages are regularly aligned, so as to suck in the excess material mass in said passages 5A of said first drum 4A, this device further comprising, as illustrated in FIG.
- un réservoir 11 équipé de moyens de chauffage (non représentés), et de moyens d'agitation 13, permettant de porter le contenant du réservoir 11, à l'état fluide,  a tank 11 equipped with heating means (not shown), and stirring means 13, for carrying the container of the tank 11, in the fluid state,
- un canal, ou plusieurs canaux, d'injection 3 permettant le transfert de la composition de bitume 2 fluide à l'intérieur du second tambour 4B,  a channel, or several channels, of injection 3 allowing the transfer of the fluid bitumen composition 2 inside the second drum 4B,
- un réservoir 14 dans lequel on peut introduire une composition d'additifs 15, le réservoir 14 étant relié au canal d'injection 3 au travers d'un injecteur 16 et permettant une injection de la composition d'additifs 15 dans la composition de bitume 2 au niveau du canal 3, situé en aval du réservoir 11 et en amont du double tambour 4.  a reservoir 14 in which an additive composition 15 can be introduced, the reservoir 14 being connected to the injection channel 3 through an injector 16 and allowing an injection of the additive composition 15 into the bitumen composition 2 at the channel 3, located downstream of the tank 11 and upstream of the double drum 4.
Comme décrit dans US-4,279,579, de préférence, ledit interstice est formé par un évidement dans la périphérie du second tambour 5B, le diamètre extérieur dudit évidement étant inférieur au diamètre intérieur dudit premier tambour 5A.  As described in US-4,279,579, preferably, said gap is formed by a recess in the periphery of the second drum 5B, the outer diameter of said recess being smaller than the inner diameter of said first drum 5A.
Comme décrit dans US-4,279,579, de préférence, le dispositif comprend une spatule en contact avec la périphérie du premier tambour pour pousser la matière en excès dans les premiers passages 5A, ladite spatule étant disposé dans la région de ladite interstice.  As described in US Pat. No. 4,279,579, the device preferably comprises a spatula in contact with the periphery of the first drum to push the excess material into the first passages 5A, said spatula being disposed in the region of said gap.
Comme décrit dans US-4,279,579, de préférence, le dispositif comprend un raccord serré autour de la périphérie du couvercle du premier tambour 4B pour couvrir le secteur formé par l'interstice.  As described in US Pat. No. 4,279,579, the device preferably comprises a tight fitting around the periphery of the cover of the first drum 4B to cover the sector formed by the interstice.
Comme décrit dans US-4,279,579, de préférence, le couvercle est bordé à ses extrémités longitudinales par des nervures de guidage courbe ayant un contour correspondant à celui du premier tambour. Comme décrit dans US-4,279,579, de préférence, les bandes de guidage comprennent des extrémités avant qui sont biseautées longitudinalement vers l'intérieur pour diriger le matériau en excès vers la spatule. As described in US Pat. No. 4,279,579, the cover is preferably bordered at its longitudinal ends by curved guide ribs having a contour corresponding to that of the first drum. As described in US Pat. No. 4,279,579, preferably, the guide strips comprise front ends that are bevelled longitudinally inward to direct the excess material to the spatula.
Comme décrit dans US-4,279,579, de préférence, le premier tambour 4A est capable de rotation.  As described in US-4,279,579, preferably, the first drum 4A is rotatable.
Exemples Examples
Matériel et méthodes  Material and methods
Les caractéristiques rhéologiques et mécaniques des bitumes auxquelles on référence dans ces exemples sont mesurées de la façon indiquée dans le tableau 1.  The rheological and mechanical characteristics of the bitumens referred to in these examples are measured as shown in Table 1.
Tableau 1  Table 1
La variation de la température de ramollissement bille et anneau (TBA) est mesurée selon la norme NF EN 1427 de ladite composition entre l'échantillon extrait de la partie haute du tube d'échantillon et l'échantillon extrait de la partie basse du tube d'échantillon. The variation of the ball and ring softening temperature (TBA) is measured according to the standard NF EN 1427 of said composition between the sample extracted from the upper part of the sample tube and the sample extracted from the lower part of the tube. 'sample.
Partie expérimentale : Experimental part :
La base bitume B2 est préparée à partir : The bitumen base B 2 is prepared from:
- d'une base bitume de grade 35/50, notée Bi, ayant une pénétrabilité P25 de 34 1/10 mm et une TBA de 52,6°C et disponible commercialement auprès du groupe TOTAL sous la marque AZALT® ; - a 35/50 grade bitumen base, denoted by Bi, having a penetrability P 25 34 1/10 mm and a TBA of 52.6 ° C and commercially available from TOTAL group under the trademark AZALT ®;
- de l'acide 1, 10 décanedioïque noté Additif Al.  - 1, 10 decanedioic acid noted Additive Al.
La base bitume B3 est préparée à partir :  The bitumen base B3 is prepared from:
- d'une base bitume de grade 35/50, notée Bi, ayant une pénétrabilité P25 de 34 1/10 mm et une TBA de 52,6°C et disponible commercialement auprès du groupe TOTAL sous la marque AZALT® ; - a 35/50 grade bitumen base, denoted by Bi, having a penetrability P 25 34 1/10 mm and a TBA of 52.6 ° C and commercially available from TOTAL group under the trademark AZALT ®;
- de l'acide 1, 10 décanedioïque noté Additif Al.  - 1, 10 decanedioic acid noted Additive Al.
- et N, N -éthylène-bis-stéréamide, noté Additif A2. I - Préparation des cœurs en bitume des granules de bitumes solides and N, N-ethylene-bis-stereamide, noted Additive A2. I - Preparation of bitumen cores of solid bitumen granules
Les quantités en pourcentage massique utilisées pour chaque bitume sont indiquées dans le tableau 2 ci-dessous.  The mass percentages used for each bitumen are shown in Table 2 below.
Tableau 2  Table 2
Le bitume est préparé de la manière suivante. The bitumen is prepared in the following manner.
Pour le bitume B2, on introduit la base bitume Bi dans un réacteur maintenu à 160°C sous agitation à 300 tours/min pendant deux heures. On introduit ensuite dans le réacteur l'additif Al. Le contenu du réacteur est maintenu à 160°C sous agitation à 300 tours/min pendant 1 heure. For the bitumen B 2 , the bitumen base Bi is introduced into a reactor maintained at 160 ° C. with stirring at 300 rpm for two hours. The additive Al is then introduced into the reactor. The contents of the reactor are maintained at 160 ° C. with stirring at 300 rpm for 1 hour.
Pour le bitume B3, on introduit la base bitume Bi dans un réacteur maintenu à 160°C sous agitation à 300 tours/min pendant deux heures. On introduit ensuite dans le réacteur l'additif Al et l'additif A2. Le contenu du réacteur est maintenu à 160°C sous agitation à 300 tours/min pendant 1 heure.  For the bitumen B3, the bitumen base Bi is introduced into a reactor maintained at 160 ° C. with stirring at 300 rpm for two hours. The additive Al and the additive A2 are then introduced into the reactor. The contents of the reactor are maintained at 160 ° C. with stirring at 300 rpm for 1 hour.
Afin de procéder à la préparation des cœurs de granules à partir des compositions bitumineuses décrites ci-dessus, on utilise un dispositif et un procédé tels que décrits de façon très détaillée dans le brevet US 4 279 579. Différents modèles de ce dispositif sont disponibles commercialement auprès de la société Sandvik sous le nom commercial de Rotoform. In order to proceed to the preparation of the granule cores from the bituminous compositions described above, a device and a method as described in great detail in US Pat. No. 4,279,579 are used. Various models of this device are commercially available. from Sandvik under the trade name Rotoform.
La composition bitumineuse Bi, B2 ou B3 est versée dans le réservoir 11 du dispositif 1 et maintenue à une température comprise entre 130 et 270°C. The bituminous composition Bi, B 2 or B 3 is poured into the tank 11 of the device 1 and maintained at a temperature between 130 and 270 ° C.
Une buse ou plusieurs buses d'injection 3 permet(tent) le transfert de la composition de bitume Bi, B2 ou B3 à l'intérieur du double tambour de pastillation 4 comportant un tambour externe rotatif, les deux tambours étant équipés de fentes, de buses et d'orifices permettant la pastillation de gouttes de bitume 7 au travers du premier tambour fixe et des orifices 5 présentant un diamètre compris entre 2 et 10 mm du tambour externe rotatif. Sous l'effet de la pression interne sensiblement homogène à l'intérieur du double tambour 4 du dispositif 1, les gouttes 7 de diamètre compris entre 2 et 10 mm sont pastillées de façon régulière au travers des orifices 5. Les gouttes de bitume 7 sont déposées sur la face supérieure 6A d'une bande de roulement 6, horizontale, entraînée par les rouleaux 12A et 12B, et dont une extrémité est placée sous le double tambour 4. La vitesse tangentielle VT du double tambour 4 est parallèle à la bande de roulement 6 et de même sens que la vitesse VR de la bande de roulement 6 avec VR et VT étant sensiblement identiques et présentant une vitesse VT = 3 m/minute. La bande de roulement 6 d'une longueur de 10 m et d'une largeur de 60 cm est équipée de quatre dispositif de conditionnement thermique 8 respectivement sur deux sections SI et S2 comportant des buses 8, 9 de vaporisation de l'eau, sur la face inférieure 6B de la bande de roulement 6. La section SI conditionne la bande de roulement 6 à la température ambiante (22-28°C), et la section S2 refroidit la bande de roulement à une température inférieure à 20°C. A l'extrémité de la bande de roulement opposée au double tambour 4, les gouttes de bitume 7 sont transférées vers des moyens de réception 10 consistant en un dispositif de stockage étant des « big bags ». Des granules de bitume Gi, G2 et G3 ont été respectivement obtenus à partir des bases bitumineuses Bi, B2 et B3 et selon le procédé ci-dessus décrit. Ces granules sont solides à température ambiante. A nozzle or a plurality of injection nozzles 3 makes it possible to transfer the bitumen composition Bi, B 2 or B 3 into the interior of the double pastillation drum 4 having a rotating outer drum, the two drums being equipped with slots , from nozzles and orifices for the pastillation of drops of bitumen 7 through the first fixed drum and orifices 5 having a diameter of between 2 and 10 mm from the rotating outer drum. Under the effect of the substantially homogeneous internal pressure inside the double drum 4 of the device 1, the drops 7 of diameter of between 2 and 10 mm are regularly pelletized through the orifices 5. The drops of bitumen 7 are deposited on the upper face 6A of a tread 6, horizontal, driven by the rollers 12A and 12B, and one end of which is placed under the double drum 4. The tangential velocity V T of the double drum 4 is parallel to the web 6 and in the same direction as the speed V R of the tread 6 with V R and V T being substantially identical and having a speed V T = 3 m / minute. The tread 6 with a length of 10 m and a width of 60 cm is equipped with four thermal conditioning device 8 respectively on two sections S1 and S2 comprising nozzles 8, 9 of water vaporization, on the lower face 6B of the tread 6. The section SI conditions the tread 6 at ambient temperature (22-28 ° C.), and the section S2 cools the tread at a temperature below 20 ° C. At the end of the tread opposite the double drum 4, the drops of bitumen 7 are transferred to receiving means 10 consisting of a storage device being "big bags". Granules of bitumen Gi, G 2 and G 3 were respectively obtained from the bituminous bases Bi, B 2 and B 3 and according to the method described above. These granules are solid at room temperature.
II - Méthode générale pour la préparation des granules de bitume solide selon l'invention comprenant une couche de revêtement II - General Method for the Preparation of Solid Bitumen Granules According to the Invention Comprising a Coating Layer
Les granules de bitume obtenus précédemment sont laissés à température ambiante pendant 10 à 15 minutes. Les granules ainsi formés sont recouverts à leur surface d'un composé anti-agglomérant, puis passées au tamis afin d'enlever l'excédent de composé anti-agglomérant.  The bitumen granules obtained above are left at room temperature for 10 to 15 minutes. The granules thus formed are coated on their surface with an anti-caking compound and then sieved to remove excess anti-caking compound.
Les granules de bitume Gi', G2' et G3' sont préparés à partir des granules de bitume Gi, G2 et G3 obtenus précédemment et selon la méthode décrite ci-dessus en utilisant comme composé anti-agglomérant de la silice pyrogénée, disponible commercialement sous la référence AEROSIL®200. Le pourcentage massique de l'enrobage pour les granules Gi', G2' et G3' est d'environ 1% en masse par rapport à la masse totale du bitume des granules. The granules of bitumen Gi ', G 2 ' and G3 'are prepared from the granules of bitumen Gi, G 2 and G 3 obtained above and according to the method described above using as anti-caking compound fumed silica, available commercially under the reference AEROSIL ® 200. The mass percentage of the coating for the granules Gi ', G 2 ' and G3 'is about 1% by weight relative to the total mass of the bitumen of the granules.
III - Stabilité au stockage III - Stability in storage
Essai de résistance à la charge des granules :  Load resistance test of granules:
Cet essai est mis en œuvre afin d'évaluer la résistance à la charge des granules de bitume préparés ci-dessus à une température de 65°C sous un effort en compression. En effet, cet essai permet de simuler les conditions de température et de compression des granules les uns sur les autres auxquels ils sont soumis lors du transport et/ou du stockage en vrac dans des sacs de 10 à 100 kg ou dans des Big Bag de 500 à 1000 kg ou dans des fûts de 200 kg et d'évaluer leur résistance dans ces conditions.  This test is carried out in order to evaluate the resistance to the load of the bitumen granules prepared above at a temperature of 65 ° C. under a compressive force. Indeed, this test makes it possible to simulate the temperature and compression conditions of the granules on each other to which they are subjected during transport and / or storage in bulk in bags of 10 to 100 kg or in Big Bags of 500 to 1000 kg or in drums of 200 kg and to evaluate their resistance under these conditions.
L'essai de résistance à la charge est réalisé selon le protocole suivant : 5 mL de granules sont placés dans une seringue de 20 mL puis le piston est placé sur les granules ainsi qu'une masse de 208g, représentant une force appliquée comme dans un Big Bag. Le tout est placé à l'étuve à 65°C pendant au moins 4 heures. Les observations sont répertoriées dans le tableau 3 ci-dessous.  The test of resistance to the load is carried out according to the following protocol: 5 mL of granules are placed in a syringe of 20 mL then the piston is placed on the granules as well as a mass of 208g, representing a force applied as in a Big Bag. The whole is placed in an oven at 65 ° C for at least 4 hours. The observations are listed in Table 3 below.
Tableau 3 Table 3
+++ : les granules conservent leur forme initiale et n'adhèrent pas entre eux.  +++: the granules retain their original form and do not adhere to each other.
++ : les granules n'adhèrent pas entre eux mais sont légèrement déformés.  ++: The granules do not adhere to each other but are slightly deformed.
+ : les granules adhèrent légèrement entre eux.  +: the granules adhere slightly to each other.
- : les granules sont partiellement fondus.  -: The granules are partially melted.
— : les granules sont fondus.  -: The granules are melted.
Les granules G2' et G3' présentent une très bonne résistance à une température ambiante de 60°C dans la mesure où ils conservent leur forme initiale et n'adhèrent pas entre eux. Ainsi, la manipulation et le transport/stockage desdits granules G2' et G3' seront aisés dans la mesure où les granules ne fondent pas et ne s'agglomèrent pas entre eux à température ambiante élevée. The granules G 2 'and G 3 ' have a very good resistance at an ambient temperature of 60 ° C. insofar as they retain their initial shape and do not adhere not between them. Thus, the handling and transport / storage of said granules G 2 'and G 3 ' will be easy insofar as the granules do not melt and do not agglomerate with each other at high ambient temperature.

Claims

REVENDICATIONS
1. Procédé de fabrication de matériau utilisable comme liant routier ou comme liant d'étanchéité, solide à température ambiante sous forme de granules comprenant un cœur (7) à base d'une première composition (2) et optionnellement une couche de revêtement à base d'une seconde composition, la première composition comprenant au moins un matériau choisi parmi : une base bitume, un brai, un liant clair, ce procédé comprenant la mise en œuvre d'un dispositif (1) destiné à la granulation qui comporte au moins deux tambours coaxiaux (4) et une bande de roulement horizontale (6) : un tambour intérieur fixe comportant au moins un orifice et un tambour extérieur rotatif comportant une pluralité d'orifices (5), les tambours étant placés au dessus d'une extrémité de la bande de roulement (6), horizontale, animée d'une vitesse VR, ce procédé comprenant au moins : A process for producing a material which can be used as a road binder or as a sealing binder, solid at ambient temperature in the form of granules, comprising a core (7) based on a first composition (2) and optionally a coating layer based on of a second composition, the first composition comprising at least one material chosen from: a bitumen base, a pitch, a clear binder, this process comprising the implementation of a device (1) intended for granulation which comprises at least two coaxial drums (4) and a horizontal tread (6): a fixed inner drum having at least one orifice and a rotating outer drum having a plurality of orifices (5), the drums being placed over one end of the tread (6), horizontal, driven by a speed V R , this method comprising at least:
(i) le chauffage de la première composition à une température à laquelle elle est fluide,  (i) heating the first composition to a temperature at which it is fluid,
(ii) l'introduction de la première composition (2) à l'état fluide dans le tambour intérieur du dispositif (1) de granulation,  (ii) introducing the first composition (2) in the fluid state into the inner drum of the granulation device (1),
(iii) la distribution de la première composition (2) vers l'extérieur, sous forme de gouttes (7) au travers des orifices (5) du tambour rotatif extérieur,  (iii) dispensing the first composition (2) outward, in the form of drops (7) through the orifices (5) of the outer rotary drum,
(iv) le dépôt des gouttes (7) sur la bande de roulement (6), et  (iv) depositing the drops (7) on the tread (6), and
(v) optionnellement l'enrobage des gouttes (7) par la seconde composition.  (v) optionally coating the drops (7) with the second composition.
Procédé selon la revendication 1, qui comprend en outre, après l'étape (iv) entre les étapes (iv) et (v), une étape (iv') de refroidissement des gouttes (7) de la première composition (2). The method of claim 1, which further comprises, after step (iv) between steps (iv) and (v), a step (iv ') of cooling the drops (7) of the first composition (2).
3. Procédé selon la revendication 2, dans lequel le refroidissement (iv') est réalisé au moyen d'un gradient de température sur la bande de roulement (6). 3. Method according to claim 2, wherein the cooling (iv ') is carried out by means of a temperature gradient on the tread (6).
4. Procédé selon la revendication 3, dans lequel la bande de roulement (6) est conditionnée à des températures différentes sur plusieurs sections (SI), ...(Si) de son parcours, avec i un entier allant de 2 à 8, de préférence de 2 à 4 par des moyens de conditionnement thermique (8,9). 4. Method according to claim 3, wherein the tread (6) is conditioned at different temperatures on several sections (SI), ... (Si) of its course, with i an integer ranging from 2 to 8, preferably from 2 to 4 by thermal conditioning means (8, 9).
5. Procédé selon l'une quelconque des revendications précédentes, dans lequel le tambour extérieur rotatif du dispositif (1) comporte des orifices (5) de diamètre allant de 2 à 10 mm, de préférence de 2 à 8 mm, de préférence de 3 à 7 mm, encore mieux de 3,5 à 6 mm. 5. Method according to any one of the preceding claims, wherein the rotary outer drum of the device (1) has orifices (5) with a diameter ranging from 2 to 10 mm, preferably from 2 to 8 mm, preferably from 3 to to 7 mm, even better from 3.5 to 6 mm.
6. Procédé selon l'une quelconque des revendications précédentes, dans lequel à l'étape (i) la première composition (2) est portée à une température allant de 100 à 270°C, de préférence de 100 à 180 °C, de préférence de 120 à 160°C, encore mieux de 130 à 150 °C. 6. Process according to any one of the preceding claims, wherein in step (i) the first composition (2) is brought to a temperature ranging from 100 to 270 ° C, preferably from 100 to 180 ° C, of preferably from 120 to 160 ° C, more preferably from 130 to 150 ° C.
7. Procédé selon l'une quelconque des revendications précédentes, dans lequel la vitesse VR de la bande de roulement (6) est inférieure à 4 m/min. 7. Method according to any one of the preceding claims, wherein the speed V R of the tread (6) is less than 4 m / min.
8. Procédé selon l'une quelconque des revendications précédentes, dans lequel le matériau utilisable comme liant routier ou comme liant d'étanchéité est choisi parmi : une composition de bitume, un brai, un liant clair, une solution-mère bitume/polymère, une solution mère liant clair/polymère. 8. Process according to any one of the preceding claims, in which the material that can be used as a road binder or as a sealing binder is chosen from: a bitumen composition, a pitch, a clear binder, a bitumen / polymer stock solution, a clear binder / polymer stock solution.
9. Procédé selon l'une quelconque des revendications précédentes, dans lequel la première composition comprenant au moins un matériau choisi parmi : une base bitume, un brai, un liant clair, une composition bitume/polymère, une composition liant clair/polymère, une solution-mère bitume/polymère ; une solution- mère liant clair/polymère ; un mélange de ces matériaux. 9. A method according to any one of the preceding claims, wherein the first composition comprising at least one material selected from: a bitumen base, a pitch, a clear binder, a bitumen / polymer composition, a clear binder / polymer composition, a bitumen / polymer master solution; a clear binder / polymer stock solution; a mixture of these materials.
10. Procédé selon l'une quelconque des revendications précédentes, dans lequel la première composition (2) comprend en outre au moins un additif chimique choisi parmi : un composé organique, une paraffine, un acide polyphosphorique et leurs mélanges. 10. A method according to any one of the preceding claims, wherein the first composition (2) further comprises at least one chemical additive selected from: an organic compound, a paraffin, a polyphosphoric acid and mixtures thereof.
11. Utilisation du procédé selon l'une quelconque des revendications précédentes pour fabriquer une composition de matériau utilisable comme liant routier ou comme liant de revêtement, solide à température ambiante, qui présente une stabilité au transport et au stockage à une température allant de 20 à 80°C pendant une durée supérieure ou égale à 2 mois, de préférence supérieure ou égale à 3 mois. 11. Use of the method according to any one of the preceding claims for manufacturing a material composition usable as a road binder or as a coating binder, solid at room temperature, which has a stability in transport and storage at a temperature ranging from 20 to 80 ° C for a period greater than or equal to 2 months, preferably greater than or equal to 3 months.
12. Dispositif utilisable pour la mise en œuvre d'un procédé selon l'une quelconque des revendications 1 à 11 , qui comprend au moins : un premier tambour cylindrique (4A) disposé au-dessus de la bande de roulement (6) et capable d'une rotation autour d'un axe longitudinal (X-X), ledit premier tambour (4A) comprenant une pluralité de premiers passages (5A) à travers la périphérie du tambour (4A, un second tambour cylindrique (4B) coaxial du premier tambour (4A), comportant des moyens (17) permettant d'admettre longitudinalement dans ledit second tambour (4B) la masse à extruder et comportant sur une partie de sa paroi (19) une pluralité de seconds passages (5B) dirigés vers la bande de roulement (6) et alignés radialement avec lesdits premiers passages (5 A), ladite partie de paroi (19) étant disposée de façon adjacente audit premier tambour (4A), ledit premier tambour (4A) étant monté pour permettre sa rotation continue sur 360 ° autour de l'axe longitudinal (X-X) par rapport audit deuxième tambour (4B) de telle sorte que la rotation relative entre lesdits tambours (4A) et (4B) produit de façon séquentielle un défaut d'alignement et un alignement des premiers passages (5A) et seconds passages (5B) pour permettre à la masse fluide de se déplacer radialement vers l'extérieur à travers les passages alignés, (5 A), (5B) et sur la bande de roulement (6A), ce dispositif comprenant en outre : 12. Device usable for the implementation of a method according to any one of claims 1 to 11, which comprises at least: a first cylindrical drum (4A) disposed above the tread (6) and capable a rotation about a longitudinal axis (XX), said first drum (4A) comprising a plurality of first passages (5A) through the periphery of the drum (4A), a second coaxial cylindrical drum (4B) of the first drum ( 4A), comprising means (17) for admitting longitudinally in said second drum (4B) the mass to be extruded and having on a part of its wall (19) a plurality of second passages (5B) directed towards the tread (6) and radially aligned with said first passages (5A), said wall portion (19) being disposed adjacent said first drum (4A), said first drum (4A) being mounted to allow continuous rotation thereof over 360 ° around the longitudinal axis (XX) p ar to said second drum (4B) such that the relative rotation between said drums (4A) and (4B) sequentially produces misalignment and alignment of the first passages (5A) and second passages (5B) for allowing the fluid mass to move radially outward through the aligned passages (5A), (5B) and on the tread (6A), which device further comprises:
- un réservoir 11 équipé de moyens de chauffage, et de moyens d'agitation (13), - un canal, ou plusieurs canaux, d'injection (3) permettant le transfert de la composition contenue dans le réservoir (11) à l'intérieur du second tambour 4B au travers des moyens d'admission (17),  a reservoir 11 equipped with heating means, and stirring means (13), a channel, or several injection channels (3) allowing the transfer of the composition contained in the reservoir (11) to the inside the second drum 4B through the admission means (17),
ce dispositif étant caractérisé en ce qu'il comprend :  this device being characterized in that it comprises:
- un réservoir (14) dans lequel on peut introduire une composition d'additifs (15), le réservoir (14) étant relié au canal d'injection (3) au travers d'un injecteur (16) et permettant une injection de la composition d'additifs (15) dans la composition de bitume (2) au niveau du canal d'injection (3), situé en aval du réservoir (11) et en amont du double tambour (4).  a reservoir (14) into which an additive composition (15) can be introduced, the reservoir (14) being connected to the injection channel (3) through an injector (16) and allowing an injection of the additive composition (15) in the bitumen composition (2) at the injection channel (3), located downstream of the tank (11) and upstream of the double drum (4).
EP17780793.0A 2016-09-08 2017-09-05 Method for manufacturing material in the form of granules that can be used as road binder or sealing binder and device for manufacturing same Pending EP3509735A1 (en)

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FR1658335A FR3055568B1 (en) 2016-09-08 2016-09-08 PROCESS FOR MANUFACTURING MATERIAL IN THE FORM OF GRANULES FOR USE AS A ROAD BINDER OR SEALING BINDER AND DEVICE FOR MANUFACTURING THE SAME
PCT/FR2017/052346 WO2018046837A1 (en) 2016-09-08 2017-09-05 Method for manufacturing material in the form of granules that can be used as road binder or sealing binder and device for manufacturing same

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