EP3509735A1

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

Info

Publication number: EP3509735A1
Application number: EP17780793.0A
Authority: EP
Inventors: Soenke Schroeder; Mouhamad MOUAZEN
Original assignee: Total Marketing Services SA
Current assignee: TotalEnergies Onetech SAS
Priority date: 2016-09-08
Filing date: 2017-09-05
Publication date: 2019-07-17
Also published as: US11198105B2; WO2018046837A1; FR3055568A1; US20190209989A1; FR3055568B1

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

METHOD OF MANUFACTURING PELLET MATERIAL FOR USE AS A ROAD OR BINDER

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.

State of the art

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.

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.

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.

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.

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.

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 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.

Application WO2009 / 153324 describes bitumen granules produced by coextrusion of a bitumen base and a polymeric anti-caking composition, in particular polyethylene.

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 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.

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. 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.

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.

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.

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.

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.

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.

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.

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.

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.

Summary of the invention

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) heating the first composition to a temperature at which it is fluid,

(ii) introducing the first composition in the fluid state into the inner drum of the granulation device,

(iii) dispensing the first composition outward, in the form of drops through the orifices of the outer rotary drum,

(iv) the deposition of the drops on the tread, and

(v) optionally, the coating of the drops by the second 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.

According to a preferred embodiment, the cooling (iv ') is carried out by means of a temperature gradient on the tread.

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.

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.

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.

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. .

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.

According to a preferred embodiment, the speed V _R of the tread is less than 4 m / min.

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.

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 .

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.

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.

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.

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.

According to a still preferred embodiment, 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 ;

mixtures of such compounds. According to a preferred embodiment, the second composition comprises from 10 to

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.

According to a preferred embodiment, the second composition consists essentially of one or more anti-caking compounds.

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.

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.

According to a preferred embodiment, the first composition comprises:

from 30 to 40%) of at least one polymer,

from 4 to 6% of at least one compatibilizing agent,

from 3% to 15% of at least one anti-caking agent,

the percentages being in mass relative to the total mass of the first composition.

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.

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 tank equipped with heating means, and stirring means,

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,

this device being characterized in that it comprises:

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

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

detailed description

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.

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.

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.

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.

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.

"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.

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.

The process

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.

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.

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.

According to a first embodiment of the invention, the coating composition, or second composition, comprises one or more anti-caking compounds.

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.

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 granules:

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).

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.

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:

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.

Preferably, the bitumen granules are prepared from a first bitumen composition comprising:

one or more bitumen bases,

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,

the percentages being in mass relative to the total mass of bitumen base.

The bitumen base and the chemical additive are as described below.

Preferably, the bitumen granules are prepared from a first bitumen composition comprising: one or more bitumen bases,

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,

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.

According to another preferred embodiment, the granules are prepared from a first composition comprising:

- one or more bitumen bases,

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,

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,

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:

- one or more bitumen bases,

from 30 to 40%) of at least one polymer,

from 4 to 6% of at least one compatibilizing agent,

from 3% to 15% of at least one anti-caking agent,

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.

According to this embodiment, 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.

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.

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:

a heart prepared from a first composition,

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.

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.

Advantageously, the various embodiments described above for the granules can be combined with one another. Second variant:

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.

According to a first embodiment, the granules consist of a first composition based on pitch.

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.

According to a second 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 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, and

at least one chemical additive chosen from an organic compound, a paraffin, a polyphosphoric acid and their mixtures.

Preferably, according to this second embodiment, the first composition comprises:

at least one bitumen base, and

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,

According to a first variant of this second embodiment, 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 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,

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

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.

According to a second variant of this second embodiment, the first composition comprises:

at least one bitumen base,

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

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,

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.

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.

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.

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%.

Third variant:

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.

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.

Therefore, for all the above applications, it is preferred to use clear synthetic binders, not containing asphaltenes and can be colored.

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.

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.

According to one embodiment of the invention, the first composition comprises - at least one clear binder base,

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.

In this case the first composition is called clear concentrated binder.

According to a preferred embodiment, the granules are prepared from a first composition comprising:

one or more clear binder bases,

from 30 to 40%) of at least one polymer,

from 4 to 6% of at least one compatibilizing agent,

from 3% to 15% of at least one anti-caking agent,

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.

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.

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:

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 bitumen base

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:

one or more bitumen bases, and

optionally at least one chemical additive.

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.

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.

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.

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.

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.

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).

The clear binder base

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.

According to one embodiment of the invention, the clear binder base comprises:

a plasticizing agent, for example a natural or synthetic oil, free of asphaltenes,

a structuring agent, for example a hydrocarbon or vegetable resin, a copolymer,

where appropriate, 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.

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.

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.

As 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.

As 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

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) 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) a copolymer based on conjugated diene units and aromatic monovinyl hydrocarbon units, for example based on a butadiene unit and on styrene units.

Preferably, the oil is a synthetic oil derived from deasphalting unit cuts (or "DAO oil").

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.

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.

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.

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.

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.

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.

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.

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%.

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. %.

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.

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.

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.

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) 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) 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) optionally adding a dope of adhesiveness, mixing and heating at a temperature between 140-200 ° C, for example, from 5 minutes to 20 minutes.

The order of steps (i) to (iv) can be changed.

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.

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.

Pitch

According to the French dictionary, "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".

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.

It is possible to obtain "oil pitch" by two methods:

l ^st method:

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.

2 ^nd process:

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".

According to one embodiment, the pitch is an oxidized pitch.

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.

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).

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.

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.

The plasticizer

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.

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.

In a preferred embodiment of the invention, the oils of petroleum origin are chosen from aromatic oils or oils of synthetic origin.

Preferably, the aromatic oils comprise aromatic extracts of petroleum residues, obtained by extraction or dearomatization of residues of distillations of petroleum fractions.

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).

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).

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").

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%. %.

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%.

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) a total content of paraffinic compounds of between 50% and

90%;

(ii) a total content of naphthenic compounds of between 5% and 25%, for example between 15% and 25%; and

(iii) a total content of aromatic compounds of between 5% and 25%, for example between 10% and 15%.

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%;

(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.

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.

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.

The structuring agent

By "structuring agent" is meant 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. For example, it may be a thermoplastic resin polycycloaliphatic, for example hydrogenated cyclopentadiene homopolymers, low molecular weight.

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.

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.

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.

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.

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).

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.

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 .

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.

The polymer

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,

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.

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.

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. 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.

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.

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.

Compatibilizing agent Preferably 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

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.).

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.

Coloring agents

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.

The chemical additive

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.

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.

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 .

In this first embodiment, according to a first variant, the organic compound is a compound of general formula (I):

Ar1-R-Ar2 (I),

in which :

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. Preferably, R is in the para position with respect to a hydroxyl group of Ar1 and / or Ar2.

Advantageously, the compound of formula (I) is 2 ', 3-bis [(3- [3, 5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide.

According to a second variant of this first embodiment, the organic compound is a compound of general formula (II):

R- (NH) _n CONH- (X) _m -NHCO (NH) _n -R '(II), wherein

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 carbon atoms, optionally substituted, and optionally comprising hetero atoms, rings and / or heterocycles;

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.

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.

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.

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.

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 '.

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:

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.

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.

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.

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)

wherein R, R ', m and X have the same definition as above.

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} .

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.

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.

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 .

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 .

Preferably, according to a second variant, the compound of general formula (II) is chosen from those of formula (IIB):

R-CONH-R '(IIB)

in which R and R 'have the same definition as above.

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.

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.

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 .

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 .

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),

in which,

- 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:

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:

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.

Other preferred compounds corresponding to formula (III) are such that: y is 0 and Z is Z _ls the compounds then have the formula:

with R selected from the following groups, taken alone or in mixtures

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.

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.

Advantageously, according to this variant, the organic compound is a compound which comprises at least one function of general formula (IV):

(IV)

With:

- x is an integer,

- 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. 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:

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:

where Ari and Ar ₂ are optionally substituted aromatic rings.

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.

According to a fifth variant of this embodiment, the organic compound is a compound of general formula (V): R "- (COOH) _z (V),

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.

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.

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.

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 .

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.

Advantageously, 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 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.

According to a sixth variant of this embodiment, the organic compound is a compound of general formula (VI):

^ (CH ₂ ) _p ^

O

(VI) wherein,

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

. (CH ₂

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.

Among the preferred organic compounds of formula (VI), there may be mentioned the following compounds:

Preferably, according to this variant, the organic compound of general formula

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)

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.

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.

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.

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.

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 and in particular q is from 3 to 20 or more and that 5q + r-2s = 0.

In particular, said polyphosphoric acids may be linear compounds of formula P _q H (q _{+ 2)} O (3q + 1) corresponding to the structural formula:

Where q has the definition given above. They can still be products of two-dimensional or three-dimensional structure.

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.

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.

According to an advantageous embodiment, the first composition comprises at least two chemical additives.

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.

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).

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).

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).

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 .

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.

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.

Preferably, and according to this second variant, the first chemical additive of formula (II) is chosen from the chemical additives of formula (IIA).

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.

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).

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).

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.

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).

Preferably, and according to this fourth variant, the second chemical additive of formula (II) is chosen from the chemical additives of formula (II A).

More preferably, and according to this fourth variant, the second chemical additive of formula (II) is N, N'-ethylenedi (stearamide).

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).

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.

Advantageously, and still according to this fourth variant, the second chemical additive of formula (V) is sebacic acid or 1,10-decanedioic acid.

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

According to one embodiment of the invention, 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.

(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) 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.

(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.

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.

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.

We prefer the combination in which the chemical additive is of formula (II) where m = 0, more preferably where m = 0 and n = 0.

The combination in which the olefinic polymer adjuvant is selected from the (b) ethylene / monomer A / monomer B terpolymers described above is also preferred.

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.

The anti-caking compound:

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.

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.

Preferably, the anti-caking compound is chosen from silica fumes.

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

By "fumed silica" is meant either a fumed silica or a fumed silica derivative.

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).

Preferably, the fumed silica compound is fumed silica.

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.

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).

According to one embodiment of the invention, the fumed silica compound has an average particle size of between 5 and 50 nm.

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.

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.

Preferably, the fumed silica compound is a hydrophilic fumed silica compound.

By "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.

Various types of fumed silica compounds are described in the following patent applications and may be used in the present invention:

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,

silicas doped with potassium oxide as described in WO 2008/043635, WO 2008/022836,

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 filed in the name of Cabot Corporation.

The fumed silica compound can be used alone or as a mixture in a coating composition.

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.

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.

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.

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 ^® .

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.

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.

According to one embodiment of the invention, the core of the granules further comprises at least one fumed silica compound as defined above.

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.

Viscosifying compound:

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.

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.

Preferably, 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;

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);

mixtures of such compounds.

Advantageously, the viscosifier is chosen from:

gelling compounds, preferably of vegetable or animal origin, such as: gelatin, agar-agar, alginates, cellulose derivatives or gellan gums;

mixtures of such compounds.

The coating layer:

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.

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.

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.

Preferably, the coating layer, formed from the second composition, is solid at ambient temperature, including at elevated ambient temperature.

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.

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. .

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%.

Advantageously, when the vicosifant is a PEG, such as for example

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%.

Advantageously, when the vicosifant is a PEG, such as for example

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%.

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.

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%.

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.

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. .

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

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.

Preferably, 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:

heating the aggregates at a temperature ranging from 100 ° C. to 180 ° C., preferably from 120 ° C. to 160 ° C.,

mixing the aggregates with the road binder in a tank such as a kneader or a kneading drum,

- Obtaining mixes.

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. .

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.

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

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.

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 .

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 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.

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

Device

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.

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,

a channel, or several channels, of injection 3 allowing the transfer of the fluid bitumen composition 2 inside the second drum 4B,

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.

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.

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.

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.

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.

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.

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.

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.

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.

As described in US-4,279,579, preferably, the first drum 4A is rotatable.

Examples

Material and methods

The rheological and mechanical characteristics of the bitumens referred to in these examples are measured as shown in Table 1.

Table 1

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.

Experimental part :

The bitumen base B ₂ is prepared from:

- 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 ^®;

- 1, 10 decanedioic acid noted Additive Al.

The bitumen base B3 is prepared from:

- 1, 10 decanedioic acid noted Additive Al.

and N, N-ethylene-bis-stereamide, noted Additive A2. I - Preparation of bitumen cores of solid bitumen granules

The mass percentages used for each bitumen are shown in Table 2 below.

Table 2

The bitumen is prepared in the following manner.

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.

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.

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.

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. 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 - General Method for the Preparation of Solid Bitumen Granules According to the Invention Comprising a Coating Layer

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.

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 - Stability in storage

Load resistance test of 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.

Table 3

+++: the granules retain their original form and do not adhere to each other.

++: The granules do not adhere to each other but are slightly deformed.

+: the granules adhere slightly to each other.

-: The granules are partially melted.

-: The granules are melted.

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

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) heating the first composition to a temperature at which it is fluid,

(ii) introducing the first composition (2) in the fluid state into the inner drum of the granulation device (1),

(iii) dispensing the first composition (2) outward, in the form of drops (7) through the orifices (5) of the outer rotary drum,

(iv) depositing the drops (7) on the tread (6), and

(v) optionally coating the drops (7) with the second composition.

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. Method according to claim 2, wherein the cooling (iv ') is carried out by means of a temperature gradient on the tread (6).

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. 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. 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. 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. 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. 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. 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. 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. 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:

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),

this device being characterized in that it comprises:

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).