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    • 专利摘要:
    A solid, room-temperature, granular bitumen comprising a core and a coating layer covering all or part of the surface of the core in which: the core comprises at least one bitumen base and the coating layer comprises at least one viscosifying compound and at least one anti-caking compound. Process for the manufacture of solid bitumen at ambient temperature as well as the use of solid bitumen at ambient temperature as road binder, in particular for the manufacture of asphalt. A process for manufacturing asphalt from solid bitumen and a method for transporting and / or storing solid road bitumen at ambient temperature.
    公开号:FR3037337A1
    申请号:FR1555261
    申请日:2015-06-09
    公开日:2016-12-16
    发明作者:Regis Vincent；Mouhamad Mouazen；Laurence Lapalu
    申请人:Total Marketing Services SA；
    IPC主号:
    专利说明:

    [0001] TECHNICAL FIELD The present invention relates to a road bitumen in divided form, solid at ambient temperature. The present invention also relates to a method for preparing road bitumen at ambient temperature and its use as a road binder, especially for the manufacture of asphalt. The present invention also relates to a method for manufacturing asphalt from solid bitumen according to the invention and a method for transporting and / or storing solid road asphalt at ambient temperature according to the invention. State of the Art 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 tanker is not sufficiently insulated, the viscosity of the bitumen may increase during a trip 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.
    [0002] As an example of packaging for the cold transport currently used, mention may be made of the packaging of bitumen at room temperature in metal drums. This means is increasingly questionable from an environmental point of view because the bitumen stored in the barrels must be reheated before use as a road binder.
    [0003] However, this operation is difficult to implement for this type of packaging and the drums are a waste after use. On the other hand, the storage of bitumen at room temperature in drums leads to losses because the bitumen is very viscous and part of the product remains on the walls of the drum when transferring to the tanks of the production units of the mix. As for the handling and transportation of bituminous products in these barrels, they may prove to be difficult and dangerous if specialized drum handling equipment is not available at the conveyors or where the bitumen is used. As other 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 easy to handle. US 3,026,568 discloses bitumen granules coated with a powdery material, such as limestone powder. Nevertheless, this type of granular bitumen does not prevent the flow of bitumen, especially at high ambient temperature. The application WO2009 / 153324 describes bitumen granules coated with a polymeric anti-caking compound, in particular polyethylene. The disadvantage of this coating 20 is that it modifies the properties of the bitumen during its road application. The Applicant has therefore sought to develop bitumens capable of being subjected to high ambient temperatures without flowing, in particular bitumens in the form of granules whose adhesion and agglomeration during their transport and / or storage and / or or handling at elevated ambient temperature is reduced relative to the prior art granules. There is therefore a need to provide a road bitumen transportable and / or storable and / or manipulable at room temperature, to overcome the disadvantages of the prior art. An object of the present invention is to provide a transportable and / or storable and / or manipulable road bitumen at high ambient temperature, the properties of which are conserved over time. In particular, the object of the present invention is to provide a transportable and / or storable road bitumen for a duration greater than 2 months, preferably 3 months, and at high ambient temperature, especially at a temperature below 100 ° C. C, preferably from 20 ° C to 80 ° C. Another object of the invention is to provide an easily manipulable road bitumen, especially at high 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 roadable bitumen that is easy to handle after prolonged transport and / or storage time at high ambient temperature, especially during a transport and / or storage period of more than 2 months, preferably greater than 3 months, and at a temperature up to 100 ° C, preferably between 20 ° C and 80 ° C. An object of the present invention is to provide a road bitumen in a form that allows its flow in solid form at room temperature, so that it can be handled without loss of material. An attempt has been made to provide a road bitumen which is in a form suitable for packaging it, packaging it, transferring it to equipment, even at a high ambient temperature, without having to heat it, and without loss. of matter. The proposed bitumen is in divided form and solid at room temperature so that it solves satisfactorily the problems mentioned above. Another objective is to provide an industrial and economical process for making transportable and / or storable road bitumen at room 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 object of the invention is to provide an ecological and economical method 25 for transporting and / or storing and / or handling the road bitumen at ambient temperature, making it possible to avoid the use of additional means for maintaining the temperature of said bitumen during transport and / or storage and / or handling and to minimize the presence of waste and / or residues. SUMMARY OF THE INVENTION The subject of the invention is a room-temperature solid bitumen in the form of granules comprising a core and a coating layer in which: the core comprises at least one bitumen base and the coating layer comprises at least one viscosifying compound and at least one anti-caking compound.
    [0004] The invention also relates to a method for manufacturing a solid bitumen at room temperature in the form of granules composed of a core and a core coating layer, this process comprising: i) shaping the core from at least one bitumen base, ii) coating the core on all or part of its surface with a composition comprising at least one viscosifying compound and at least one anti-caking compound; iii) optionally, drying the granules obtained in step ii) 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.
    [0005] The invention also relates to a solid bitumen at room temperature obtainable by the implementation of this method. 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 from 80 mPa.s. -1 to 450 mPa.s-1, the viscosity being a Brookfield viscosity measured at 65 ° C. According to a preferred embodiment, the viscosifying compound is chosen from: - gelling compounds, preferably of vegetable or animal origin, such as gelatin, agar-agar, alginates, cellulose derivatives and gums; gellans; polyethylene glycols (PEG) such as PEGs having a molecular weight of between 800 g.m -1 and 8000 g.mol -1 -1; mixtures of such compounds.
    [0006] According to a preferred embodiment, the coating layer comprises at least 10% by weight of a viscosifying compound with respect to the total mass of the coating layer, preferably from 10 to 90% by weight, more preferably from 10 to 90% by weight. at 85% by weight. According to a preferred embodiment, the anti-caking compound is chosen from: talc; fines generally of diameter less than 125 mt; sand ; cement ; carbon; wood residues such as lignin, conifer needle powders and conifer cone powders; glass powder; alumina; silica; silica derivatives such as silicates, silicon hydroxides and silicon oxides; plastic powder; and their mixtures. According to a preferred embodiment, the coating layer comprises at least 10% by weight of an anti-caking compound relative to the total mass of the coating layer, preferably from 10 to 90% by weight, even more preferably from 15 to 90% by weight. 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 bitumen base further comprises at least one chemical additive selected from: an organic compound, a paraffin, a polyphosphoric acid and mixtures thereof. According to a preferred embodiment, the bitumen base has a penetrability of 5 to 45 1/10 mm, measured at 25 ° C according to EN 1426 and / or a ball and ring softening temperature greater than or equal to 90 ° C, the ball softening temperature and ring 20 being measured according to EN 1427. In a preferred embodiment, the solid bitumen at room temperature has a stability in transport and storage at a temperature ranging from 20 to 80 ° C for a longer period or equal to 2 months, preferably greater than or equal to 3 months. The invention also relates to the use of the solid bitumen defined above as a road binder. According to a preferred embodiment, the use relates to the manufacture of asphalt. The invention also relates to a method for manufacturing asphalt mixes comprising at least one road binder and aggregates, the road binder being chosen from the bitumens defined above, this process comprising at least the steps of: heating aggregates at a temperature ranging from 100 ° C to 180 ° C, preferably from 120 ° C to 160 ° C, - mixing aggregates with the road binder in a tank such as a kneader or kneading drum, 5 - obtaining asphalt. According to a preferred embodiment, the asphalt manufacturing process does not include a heating step of the road binder before mixing with the aggregates. Finally, the invention relates to a method for transporting and / or storing road bitumen, said road bitumen being transported and / or stored as solid bitumen at room temperature as defined above. DETAILED DESCRIPTION The objectives which the applicant has set for himself have been achieved by the development of bitumen compositions in a divided form, having a core / shell structure, in which the core is based on bitumen and the layer of coating gives the overall structure improved properties compared to the known bitumen granules of the prior art. A first subject of the invention relates to a solid bitumen at ambient temperature in the form of granules comprising a core and a coating layer in which: the core comprises at least one bitumen base and the coating layer comprises at least one viscosifying compound and at least one anti-caking compound. By "ambient temperature" is meant the temperature resulting from the climatic conditions in which the road bitumen is transported and / or stored. More precisely, the ambient temperature is equivalent to the temperature reached during the transport and / or the storage of the road bitumen, it being understood that the ambient temperature implies that no heat input is brought other than that resulting from the climatic conditions. The invention relates to bitumens capable of being subjected to a high ambient temperature, in particular a temperature of up to 100 ° C, preferably from 20 ° C to 80 ° C. 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 which retains its solid appearance throughout transport and / or storage at ambient temperature, that is to say a bitumen which does not flow at temperature. ambient under its own weight and more, which does not flow when subjected to pressure forces from transport conditions and / or storage. By "coating layer covering at least part of the surface of the core" is meant that the coating layer covers at least 90% of the surface of the core, preferably at least 95% of the core area, more preferably at least less than 99% of the surface of the heart. The expression "consists essentially of" followed by one or more features means that may be included in the process or material of the invention, in addition to the components or steps explicitly listed, components or steps that do not alter significantly the properties and characteristics of the invention. - The 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 that 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 from 50 mPa.s-1 to 550 mPa.s-1, more preferably 80 mPa. s-1 at 450 mPa.s-1, the viscosity being a Brookfield viscosity measured at 65 ° C. The 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 or gellan gums; polyethylene glycols (PEG), such as PEGs having a molecular weight of between 800 g / mol and 8000 g / mol, for example a PEG having a molecular weight of 800 g / mol (PEG); 800), a PEG having a molecular weight of 1000 g.mol -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.mo1-1 (PEG-4000) or PEG having a molecular weight of 6000 g.mo1-1 (PEG-6000); mixtures of such compounds. 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 to each other during their transport and / or storage at temperature. ambient and which ensures their fluidity during their handling. More preferably, the anti-caking compound is chosen from: talc; fines generally of diameter less than 125 mt; sand ; cement ; carbon; wood residues such as lignin, conifer needle powders and conifer cone powders; glass powder; alumina; silica; silica derivatives such as silicates, silicon hydroxides and silicon oxides; plastic powder; and their mixtures. Advantageously, the anti-caking compound is chosen from: fines, generally less than 125 μm in diameter; wood residues such as lignin, conifer needle powders and conifer cone powders; their mixtures. The coating layer According to one embodiment of the invention, the coating layer is obtained by applying a composition comprising at least one viscosifying compound and at least one anti-caking compound on all or part of the surface. from the heart of solid bitumen. Preferably, the coating layer is solid at room temperature, including at elevated ambient temperature. Preferably, the 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 a Brookfield viscosity.
    [0007] Preferably, the coating layer comprises at least 10% by weight of a viscosifying compound relative to the total mass of the coating layer, 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 coating layer comprises from 10 to 90% by weight of viscosifying compound with respect to the total mass of the coating layer, preferably from 15 to 85% by weight. %, even better from 15 to 60%. Advantageously, when the vicosifier is a gelling agent, such as, for example, gelatin, the coating layer comprises from 10 to 90% by weight of anti-agglomerating compound with respect to the total weight of the coating layer, preferably 15 to 85%, even better from 40 to 85%. Advantageously, when the vicosifier is a PEG, such as for example a PEG having a molecular weight of between 800 gm-1 and 8000 gm-1, the coating layer comprises from 10 to 90% by weight of viscosifying compound. relative to the total mass of the coating layer, preferably 40 to 90%, more preferably 60 to 90%. Advantageously, when the vicosifier is a PEG, such as for example a PEG having a molecular weight of between 800 g.mol -1 and 8000 g.mol -1, the coating layer comprises from 10 to 90% by weight of anti-aging compound. agglomerating with respect to the total mass of the coating layer, preferably from 10 to 60%, more preferably from 10 to 40%. Preferably, the coating layer comprises at least 10% by weight of an anti-caking compound relative to the total mass of the coating layer, preferably from 10 to 90% by weight, even more preferably from 15 to 90% by weight. in mass. Preferably, the coating layer is at least 5% by weight based on the total mass of the granule, preferably 10 to 60% by weight, more preferably 10 to 50%. In addition to the viscosifying compound and the anti-caking compound, the coating layer may optionally comprise one or more compounds chosen from: chemical additives, polymers, etc.
    [0008] Advantageously, the viscosifying compound and the anti-caking compound represent at least 90% by weight relative to the total weight of the coating layer, more preferably at least 95% by weight and advantageously at least 98% by weight. According to a preferred embodiment, the coating layer consists essentially of the viscosifying compound and the anti-caking compound. The granules: According to the invention, the solid bitumen at room temperature is packaged in a divided form, that is to say in the form of small units, which are called granules or particles, comprising a bitumen-based core and an envelope or shell or coating or coating layer or coating.
    [0009] Preferably, the granules of solid bitumen according to the invention may have within the same population of granules, one or more forms chosen from a cylindrical, spherical or ovoid shape. The size of the bitumen granules is such that the longest average dimension is preferably less than or equal to 50 mm, more preferably from 3 to 30 mm, more preferably from 5 to 20 mm. The size and shape of the bitumen granules may vary depending on the manufacturing process employed. For example, the use of a die makes it possible to control the manufacture of granules of a chosen size. Sieving allows the selection of granules according to their size.
    [0010] Preferably, the bitumen granules 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. Without being bound to the theory, the Applicant has unexpectedly discovered that the combination of a viscosifying compound according to the invention and an anti-caking compound according to the invention makes it possible to obtain a coating layer which is resistant to the climatic conditions and to the conditions of transport and / or storage of the solid road bitumen, which breaks easily under a mechanical shearing effect, as for example under the effect of a mechanical shear applied in a tank such as a kneader or drum-kneader during the manufacture of asphalt.
    [0011] More particularly, the coating layer is resistant to the transport and / or storage of bitumen at room temperature in "Big Bags" while being brittle under the effect of mechanical shear. It thus allows the release of the bitumen core during the manufacture of asphalt. According to one embodiment of the invention, the solid bitumen 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. . According to a particularly preferred embodiment of the invention, the solid bitumen has: a core comprising at least one bitumen base and a coating layer comprising gelatin or PEG and at least one anti-caking compound selected among the fines generally of diameter less than 125; wood residues such as lignin, conifer needle powders and conifer cone powders; and their mixtures. More preferably, the solid bitumen has: a core comprising at least one bitumen base and a coating layer comprising gelatin or PEG and at least one anti-caking compound comprising lignin.
    [0012] According to a still more advantageous embodiment, the solid bitumen essentially consists of: a core consisting of a bitumen base and a coating layer consisting of a mixture of gelatin or a PEG, with lignin. Advantageously, the core or core of the solid bitumen granules according to the invention is prepared from road bitumen, said road bitumen being prepared by bringing into contact: one or more bitumen bases, and optionally at least one a 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. By "bitumen" or "road bitumen" is meant 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 can be optionally visbroken and / or deasphalted and / or rectified in air. Vacuum distillation of atmospheric residues from atmospheric distillation of crude oil is common. This manufacturing process therefore corresponds to the succession of an atmospheric distillation and a vacuum distillation, 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 makes it possible to obtain a blown, or semi-blown or oxidized or air-honed or partially rectified air-based base. 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 the conventional processes for the production of bitumen bases, production temperatures of between 100 ° C. and 200 ° C., preferably between 140 ° C. and 200 ° C., more preferably between 140 ° C. and 170 ° C, and with stirring for a period of at least 10 minutes, preferably between 30 minutes and 10 hours, more preferably between 1 hour and 6 hours. The 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.
    [0013] 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 EN 1426 from 25 to 330 1/10 mm, preferably from 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 penetration with the needle, 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).
    [0014] The bitumen base 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 bitumen comprises at least one chemical additive, the target penetrability for the additivated bitumen base is preferably 5 to 45 1/10 mm and / or the target ball and ring softening temperature (TBA) is Preferably, greater than or equal to 90 ° C., it being understood that the penetrability is measured at 25 ° C. according to EN 1426 and the TBA according to EN 1427. Preferably, the organic compound has a molar mass of less than or equal to 2000. gmol-1, preferably a molar mass less than or equal to 1000 gmol-1.
    [0015] In this embodiment, the organic compound is a compound of the general formula Ar1-R-Ar2 (I), wherein: - An and Ar2 independently of one another represent a benzene ring or a ring system; condensed aromatic rings 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 amide group and / or ester.
    [0016] Preferably, An 1 and / or Ar 2 are 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 An and Ar2 are 3,5-dialkyl-4-hydroxyphenyl groups, preferably 3,5-di-tert-butyl-4-hydroxyphenyl groups. Preferably, R is in the para position with respect to a hydroxyl group of An 1 and / or Ar 2. Advantageously, the compound of formula (I) is 2 ', 3-bis [(3- [3, 5-di-tert-butyl] -4-hydroxyphenyl] propionyl]] propionohydrazide. According to another variant of this embodiment, the organic compound is a compound of general formula (II): ## STR5 ## wherein the groups R and R ', which may be identical or different, contain a saturated or unsaturated, linear, branched or cyclic hydrocarbon-based chain containing from 1 to 22 carbon atoms, which may be substituted, and optionally comprising hetero atoms, rings and rings; 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 m has a value of 0, then the groups R (NH) .CONH and NHCO (NH) .- R 'are covalently linked by a CONH-NHCO hydrazide bond. The group R or the group R 'then comprises a group chosen from at least one hydrocarbon chain of at least 4 carbon atoms, at least one aliphatic ring of 3 to 8 atoms, at least one aliphatic condensed polycyclic system, partially aromatic or wholly aromatic, each ring comprising 5 or 6 atoms, taken alone or as a mixture. 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 a group chosen from at least one hydrocarbon chain of at least 4 carbon atoms. at least one aliphatic ring of 3 to 8 atoms, at least one aliphatic condensed polycyclic system, partially aromatic or wholly aromatic, each ring comprising 5 or 6 atoms, taken alone or as a mixture.
    [0017] Preferably, the group R and / or R 'comprises an aliphatic hydrocarbon chain of 4 to 22 carbon atoms, especially chosen from C4H9, C5H11, C91-119, C111-123, C12H25, C17H35, C18H37 and C21H43 groups. , C22H45. 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. Preferably, the group X can also be a cyclohexyl group or a phenyl group, the radicals R- (NH) .CONH- and NHCO (NH) .- R ' - can then be in ortho, meta or para position. Moreover, they can be in cis or trans position relative to each other. In addition, when the radical X is cyclic, this ring may be substituted with other groups than the two main groups R- (NH) .CONH- and -NHC 0. 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 3037337 is a group comprising two aliphatic rings connected by an optionally substituted CH2 group such as, for example: Advantageously, the organic compound is a compound of general formula (II) chosen from hydrazide derivatives such as C5H11-CONH-NHCO-05H11, C91119-CONH-NHCO-C9H19, C11H23-CONH-NHCO-C11H23, C17H35-CONH-NHCO-C17E135, or C21H43-CONH-NHCO-C21H43; diamines such as N, N'-ethylenedi (stearamide) of the formula C17E135-CONH-CH2-CH2-NHCO-C17E135; and ureide derivatives such as 4,4'-bis (dodecylaminocarbonylamino) diphenylmethane of formula C12H25-NHCONH-C6H4-CH2-C6H4-NHCONH-C12H25. According to another variant of this embodiment, the organic compound is a compound of formula (III): ## STR2 ## wherein R ', which may be identical or different, contain a saturated or unsaturated, linear, branched or cyclic hydrocarbon chain comprising 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: ## EQU1 ## and y are different integers with a value ranging from 0 to 3 and such that x + y = 3. Preferably, when x is 0 and Z is Z2, the compound of formula (III) is N2, N4, N6-tridecylmelamine having the following formula with R 'representing C9H19: ## STR2 ## Other preferred compounds corresponding to formula (III) are such that x is equal to 0, Z represents Z2 and R 'represents a linear saturated hydrocarbon-based chain of 1 to 22 carbon atoms, of which X is 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 Z1, the compounds then have the formula: H with R selected from the following groups, taken alone or in mixtures: Other preferred compounds of formula (III) are such that: y is 0, Z is Z1 and R is a linear saturated hydrocarbon chain of 1 to 22 carbon atoms, preferably 8 to 12 carbon atoms. carbon. According to another variant of this embodiment, the organic compound of general formula (IV) is a derivative of sorbitol. By "sorbitol derivative" is meant any reaction product, obtained from sorbitol. In particular, 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 derivatives of sorbitol may thus be all the condensation products of aldehydes, especially aromatic aldehydes with sorbitol. Sorbitol derivatives of the general formula will then be obtained: where Ar 'and Ar2 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: 2,4: 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 -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, the organic compound is 1,3: 2,4-Di-O-benzylidene-D-sorbitol. In place of sorbitol, it could be envisaged to use any other polyhydric alcohol such as, for example, xylitol, mannitol and / or ribitol. According to another variant of this embodiment, the organic compound is a compound of general formula (V): R "- (COOH), (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 4.
    [0018] Preferably, the group R "is preferably a linear saturated chain of formula Cw1-12 ,, with w an integer ranging from 4 to 22, preferably from 4 to 12. According to this variant of the invention, the Organic compounds of formula (V) can be diacids (z = 2), triacids (z = 3) or tetracides (z = 4) Preferred organic compounds are diacids with z = 2. the diacids have the general formula HOOC-CwH2w-COOH with w an integer ranging from 4 to 22, preferably from 4 to 12 and where z = 2 and R "= CwH2w. Advantageously, 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 = 10 5, suberic acid or acid 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. The diacids can also be unsaturated fatty acid (s) diacid dimers, that is to say dimers formed from at least one unsaturated fatty acid, for example from a single unsaturated fatty acid 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 Alder 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 C8 to C34, especially C12 to C22, in particular C16 to C20, and more particularly to C18. 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 another variant of this embodiment, the organic compound is a compound of general formula (VI): ## STR2 ## in which, groups Y and Y 'represent independently of one another an atom or group selected from: H, - (CH2) q-CH3, - (CH2) q -NH2, - (CH2) q-OH, - (CH2) qCOOH or (C H2) p 5 - (C H2 wherein q is an integer ranging 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 Among the preferred organic compounds having formula (VI), there may be mentioned the following compounds: ## STR2 ## Preferably, the organic compound of general formula (VI) is: HN o According to another 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', identical or different, represent a chain hy saturated or unsaturated, linear, branched or cyclic hydrocarbon containing from 1 to 22 carbon atoms, preferably from 8 to 12 carbon atoms, optionally substituted, and optionally comprising hetero atoms, rings and / or heterocycles . In this embodiment, the paraffins have chain lengths of 30 to 120 carbon atoms (C30 to C120). The paraffins are 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, the 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 advantageously, 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 polymethylene paraffins, 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 199475. According to another variant of this embodiment, the polyphosphoric acids (PPA) 25 are described in WO 97 / 14753. The content of WO 97/14753 is considered as part of the description of the present application. 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), (IV), (V), (VI) and (VII) and / or different paraffins and / or polyphosphoric acid in the bitumen base. According to one embodiment of the invention, the 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, more preferably from 0% to , 5% to 2.5% by weight of chemical additive relative to the total mass of said core.
    [0019] According to one embodiment of the invention, the core 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 selected from random or random copolymers of ethylene and a monomer selected 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 selected from random or random, preferably random, terpolymers of ethylene, a monomer A and a monomer B. The monomer A is selected from vinyl acetate and C1-C6 alkyl acrylates or methacrylates. Monomer B is selected from glycidyl acrylate and glycidyl methacrylate.
    [0020] 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 polymer substrate consists of a polymer chosen from polyethylenes, in particular low density polyethylenes, polypropylenes, statistical or random, preferably random, copolymers of ethylene and vinyl acetate and random or block copolymers, preferably statistics, ethylene and C1-C6 alkyl acrylate or methacrylate, comprising from 40% to 99.7% by weight, preferably from 50% to 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.
    [0021] Advantageously, the olefinic polymer adjuvant is chosen from among the random terpolymers of ethylene (b), a monomer A chosen from C1-C6 alkyl acrylates or methacrylates and a monomer B chosen from glycidyl acrylate and glycidyl methacrylate, comprising 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. According to one embodiment of the invention, 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, more preferably from 0.5% to 6% by weight of the olefinic polymer adjuvant relative to the total mass of said core. According to one embodiment of the invention, the core may also comprise other known additives or other known bitumen elastomers such as SB (block copolymers of styrene and butadiene) copolymers, SB S (copolymer with styrene-butadiene-styrene blocks), 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 WO11 / 013073. Another method of the invention relates to a process for manufacturing a solid bitumen at room temperature in the form of granules composed of a core and a core coating layer, this process comprising i) shaping the core from at least one bitumen base; ii) coating the core on all or part of its surface with a composition comprising at least one viscosifying compound and at least one anti-caking compound; Iii) optionally, drying the granules obtained in step ii) 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.
    [0022] Preferably, step ii) of application is by soaking, spraying, coextrusion, etc. The shaping of the core of the granules from an optionally additive bitumen base may be carried out according to any known process, for example according to the manufacturing method described in the document US Pat. No. 3,026,568, the document WO 2009/153324 or the WO 2012/168380. According to a particular embodiment, the shaping of the core of the solid bitumen can be carried out by draining, in particular by means of a drum. Other techniques can be used in the process for manufacturing the solid bitumen core, in particular molding, pelletizing, extrusion, etc.
    [0023] Preferably, the size of the solid bitumen core particles has a longest average size ranging from 1 to 30 mm, preferably from 5 to 20 mm. Preferably, during the implementation of the process of the invention, the mass ratio of the coating composition comprising at least one viscosifying compound and at least one anti-caking compound with respect to the base bitumen mass, optionally The additive forming the core is 0.1 to 1, preferably 0.2 to 0.9. Another object of the invention is a solid bitumen at room temperature in the form of granules obtainable by carrying out the process according to the invention as described above. Such solid bitumen in the form of granules advantageously has the properties described above. Uses of granules of solid bitumen Another object of the invention also relates to the use of granules of solid bitumen at ambient temperature according to the invention as described above as road binder. The road binder can be used to manufacture mixes, in combination with aggregates according to any known method.
    [0024] Preferably, the solid bitumen at ambient temperature according to the invention is used for the manufacture of bituminous mixes. 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. Examples which may be mentioned are surface coatings, hot mixes, cold mixes, cold-cast asphalts, deep emulsions, base, bonding, bonding and rolling layers, and other combinations. an asphalt binder and road aggregate having particular properties, such as anti-rutting layers, draining asphalts, or asphalts (a mixture of bituminous binder and sand-like aggregates). Another subject of the invention relates to a method for manufacturing asphalt mixes comprising at least one road binder and aggregates, the road binder being chosen from the bitumens according to the invention, this process comprising at least the steps of: heating 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 kneading drum, coated materials. The method of the invention has the advantage of being able to be implemented without any prior step of heating the solid bitumen granules. The process for manufacturing mixes according to the invention does not require a step of heating the granules of solid bitumen before mixing with the aggregates because, in contact with the hot aggregates, the solid bitumen at ambient temperature melts. The solid bitumen at ambient temperature 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.
    [0025] Preferably, the step of mixing the aggregates and road binder is carried out with stirring, then stirring is maintained for at most 5 minutes, preferably at most 1 minute to allow to obtain a homogeneous mixture. The solid bitumen in the form of granules according to the present invention is remarkable in that it allows the transport and / or storage of road bitumen at ambient temperature under optimum conditions, in particular without agglomeration and / or adhesion of solid bitumen during transport and / or storage, even when the ambient temperature is high. In addition, the coating layer of the granules breaks under the effect of contact with hot aggregates and shear and releases the bitumen base. Finally, the presence of the coating layer in the road binder and aggregate mixture does not degrade the properties of said road bitumen for road application as compared to an uncoated bitumen base. Another method of the invention also relates to a method for transporting and / or storing and / or handling road bitumen, said road bitumen being transported and / or stored and / or handled as solid bitumen granules at room temperature.
    [0026] Preferably, the road bitumen is 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 .
    [0027] The bitumen granules according to the invention have the advantage of maintaining their divided form, and therefore of being able to be handled, after storage and / or transport at a high ambient temperature. 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 conditioning to equipment as a construction equipment (tank, mixer etc ...). The bitumen granules 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 in hot melt material.
    [0028] They can 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.
    [0029] The invention is illustrated by the following non-limiting examples. Examples Materials and Methods The rheological and mechanical characteristics of the bitumens referred to in these examples are measured as shown in Table 1.
    [0030] Table 1 Property Abbreviation Unit Measuring standard Penetration at 25 ° C needle P25 1/1 0 mm NF EN 1426 Softening temperature TBA ° C NF EN 1427 ball and ring The variation of the softening temperature Ring (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 5 and the sample extracted from the lower part of the sample tube. The bitumen bases B2 to B5 are prepared from: - a 35/50 grade bitumen base, denoted B1, having a P25 penetrability of 34 1/10 mm and a TBA of 52.6 ° C. and available commercially from the TOTAL group 10 under the trademark AZALT® - a styrene / butadiene / styrene block copolymer (SBS), 30.5% by weight of styrene and 69.5% by weight of butadiene. The content of 1,2-vinyl group is 27.8% by weight relative to the total weight of copolymer. The copolymer has a weight average molecular weight (M w) of 142,500 Daltons and a polydispersity index I p of 1.09. This copolymer is commercially available from KRATON under the name D1192; a chemical additive, 2 ', 3-bis [[343,5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide, denoted hydrazide; decreic acid, decanoic acid; 20 - sulfur flower, noted crosslinking; - zinc octanoate; noted scavenger. The mass percentages used for each bitumen are shown in Table 2 below.
    [0031] Table 2 Bitumen B2 B3 B4 B5 Bi bitumen base 99.1% 98.5% 95.4% 94.8% Hydrazide 0.9% 0.9% - Acid - 1.5% - 1.5 % SBS - - 3.4% 3.4% Crosslinker 0.1 0.1 Scavenger - 0.2 0.2 P25 (1/10 mm) 17 14 22 21 TBA (° C) 107 93 34 37 The amount of Additives for each bitumen are adjusted so as to obtain bitumens having equivalent mechanical properties, in particular near P25 and TBA penetrability. The bitumens are prepared in the following manner. For the bitumen B2, the bitumen base B1 is introduced into a reactor maintained at 160 ° C. with stirring at 300 rpm for two hours. The hydrazide is then introduced into the reactor. The contents of the reactor are maintained at 160 ° C. with stirring at 300 rpm for 1 hour. Bitumen B3 is prepared from bitumen base B1 and acid in the same way as bitumen B2. For the bitumen B4, the bitumen base B1 and the SBS copolymer are introduced into a reactor maintained at 185 ° C. and with stirring at 300 rpm. The reactor contents are then maintained at 185 ° C. with stirring at 300 rpm for 4 hours. 0.1% crosslinking agent is added, the mixture is left to react for 2 hours at 185 ° C. with stirring at 300 rpm and 0.2% scavenger is added at 185 ° C. with stirring at 300 rpm for 20 minutes. The temperature is lowered to 160 ° C. with stirring at 300 rpm, and then the hydrazide is added in the form of granules. The mixture is stirred for about 1 hour at 160 ° C to obtain a homogeneous final appearance. The mixture is cooled to room temperature. Bitumen B5 is prepared as bitumen B4 using acid in place of the hydrazide. 1. Preparation of the various granules of solid bitumens G1, G2, G3, G4, G5, G6 and G7 1.1 General method for the preparation of bitumen cores of the granules according to the invention The bitumen base (B2 to B5) is heated at 160 ° C for two hours in an oven before being cast in a silicone mold having different holes of spherical shape so as to form solid bitumen hearts. After observing the solidification of the bitumen in the mold, the surplus is leveled with a heated blade Bunsen burner. After 30 minutes, the solid bitumen in the form of uncoated granules is demolded and stored in a tray 10 covered with silicone paper. The hearts are then allowed to cool to room temperature for 10 to 15 minutes. 1.2 General Method for the Preparation of Solid Bitumen Granules According to the Invention Comprising a Coating Layer (PEG-4000 and Lignin) A composition is prepared by melting the PEG-4000 in an oven at a temperature between 70 ° C. C and 80 ° C for a period of between one to two hours. Lignin is added hot with stirring in this composition. The bitumen cores previously obtained at 1.1 are stitched onto a needle before being immersed in the coating composition, still in the oven, with stirring. The coated bitumen granules are deposited on a silicone plate.
    [0032] Optionally, the coated solid bitumen granules thus obtained may be coated with an additional layer with the lignin powder. The solid bitumen granules thus obtained are left in the open air for at least 2 hours and at room temperature to solidify the coating layer. Thus, solid bitumen granules having a core / shell structure according to the invention are obtained. The amounts of PEG-4000 and lignin may vary depending on the viscosity of the desired composition. A composition C1 was prepared comprising 80% by weight of PEG-4000 and 20% by weight of lignin. 1.3 General method for the preparation of solid bitumen granules according to the invention comprising a coating layer (gelatin and lignin) The gelatin, in the form of a plate, is soaked in cold water for 10 minutes up to 80% d water absorbed and placed in an oven at 70 ° C. The lignin, previously dried at 110 ° C for two hours, is added hot in the gelatin.
    [0033] The bitumen cores previously obtained in 1.1 are stitched onto a needle before being immersed in the previously obtained coating composition, still in the oven, with stirring. The coated bitumen granules are deposited on a silicone plate.
    [0034] Optionally, the coated solid bitumen granules thus obtained may be coated with an additional layer with the lignin powder. The coated solid bitumen granules thus obtained are left in the open air for a few minutes and then are annealed at 50 ° C for a period of between one and two hours to solidify the coating layer.
    [0035] Thus, solid bitumen granules having a core / shell structure according to the invention are obtained. The amounts of gelatin, water and lignin may vary depending on the viscosity of the desired composition. Two compositions (gelatin and lignin) C2 and C3 were prepared according to Table 3: Table 3 Gelatin (% by weight) Lignin (% by weight) Water (% by weight) Composition C2 16 15 69 Composition C3 14 13 73 1.4 Preparation of different solid bitumens according to the invention A solid bitumen G1 (control test) was prepared according to the method described in point 1.1, and then powdered with lignin. G1 is composed of a bitumen core obtained by shaping the base B2 and an anti-caking layer composed of lignin. A solid bitumen G2 (control test) was prepared according to the method described in point 1.1, and then powdered with lignin. G2 is composed of a bitumen core obtained by shaping the base B3 and an anti-caking layer composed of lignin.
    [0036] A solid bitumen G3 according to the invention was prepared according to the methods described in points 1.1 and 1.2 and is composed of a bitumen core obtained by shaping the base B3 and a coating layer obtained from of the composition Cl. A solid bitumen G4 according to the invention was prepared according to the methods described in points 1.1 and 1.3 and is composed of a bitumen core obtained by shaping the base B3 and a layer coating obtained from the composition C2.
    [0037] A solid bitumen G5 according to the invention was prepared according to the methods described in points 1.1 and 1.3 and is composed of a bitumen core obtained by shaping the base B3 and a coating layer obtained at from the composition C3. A G6 solid bitumen (control test) was prepared according to the method described in 1.1 and then coated with gelatin. G6 is composed of a bitumen core obtained by shaping the base B3 and a viscosifying layer composed of PEG 4000. A solid bitumen G7 (control test) was prepared according to the method described in point 1.1 and coated with gelatin. G7 is composed of a bitumen core obtained by shaping the B3 base and a viscosity layer composed of gelatin. 2. Test of load resistance of solid bitumens G1, G2, G3, G4, G5, G6, and G7 in the form of coated granules This test is carried out in order to evaluate the resistance to loading of the granules G1 to G7 at a temperature of 50 ° C under compressive stress. 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. from 500 to 1000 kg or in drums of 200 kg and to evaluate their resistance under these conditions. The load resistance test is carried out using a texture analyzer sold under the name LF Plus by the company LLOYD Instruments and equipped with a thermal enclosure. To do this, a metal container 25 mm in diameter containing a mass of 10 g of bitumen granules is placed inside the thermal enclosure set at a temperature of 50 ° C for 1 hour. The piston of the texture analyzer is a cylinder with a diameter of 20 mm and a height of 60 mm. The cylindrical piston is initially placed in contact with the upper layer of the granules. Then, it moves vertically downwards at a constant speed of 0.5 mm / min over a calibrated distance of 5 mm so as to exert a compressive force on all the granules placed in the container. After removal of the piston, it is visually assessed the compressive strength of the granules, including their appearance and ability to agglomerate. The observations are listed in Table 4 below.
    [0038] Table 4 Granules G1 G2 G3 G4 G5 G6 G7 (control) (control) (control) (control) Holding a + + ++ +++ +++ - - the charge at 50 ° C +++: the granules retain their original form and do not adhere to each other. ++: the granules do not adhere to each other but no longer have their rounded shape. : the granules adhere slightly to each other. 5: the granules are fairly melted. : the granules are melted. The granules G3, G4 and G5 according to the invention have a very good resistance to the load at 50 ° C insofar as they do not adhere to each other. In addition, the granules G4 and G5 retain their initial shape. The granules G3, G4 and G5 are resistant to the compression and temperature conditions compared to the control granules G1, G2, G6 and G7 which will have a tendency to agglomerate and / or melt during their transport or storage, in particular to temperatures greater than or equal to 50 ° C. Thus, the manipulation of said granules G1, G2, G6 and G7 will be less easy compared to granules G3, G4 and G5. In particular, if the bitumen granules are transported in bags or big bags, the agglomerated and / or melted granules G1, G2, G6 and G7 are more likely to leak out of the bags or big bags, making handling of said bags difficult or difficult. Big bags that will stick to each other. Transferring them to field equipment can also be difficult because of their behavior. 20
    权利要求:
    Claims (17)
    [0001]
    REVENDICATIONS1. Bitumen solid at ambient temperature in the form of granules comprising a core and a coating layer in which: the core comprises at least one bitumen base and the coating layer comprises at least one viscosifying compound and at least one anti-caking compound .
    [0002]
    Bitumen according to claim 1, in which 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 from 80 mPa.s 1 to 450 mPa.s-1, the viscosity being a Brookfield viscosity measured at 65 ° C.
    [0003]
    3. Bitumen according to claim 1 or 2, wherein the viscosifying compound is chosen from: - gelling compounds, preferably of plant or animal origin, such as gelatin, agar-agar, alginates, derivatives of cellulose and gellan gums; polyethylene glycols (PEG) such as PEGs having a molecular weight of between 800 g.m -1 and 8000 g.mol -1 -1; mixtures of such compounds.
    [0004]
    Bitumen according to any one of the preceding claims, wherein the coating layer comprises at least 10% by weight of a viscosifying compound with respect to the total mass of the coating layer, preferably from 10 to 90% by weight. mass, more preferably from 10 to 85% by weight.
    [0005]
    Solid bitumen according to any one of the preceding claims, wherein the anti-caking compound is selected from: talc; fines generally of diameter less than 125 mt; sand ; cement ; carbon; wood residues such as lignin, conifer needle powders and conifer cone powders; glass powder; alumina; silica; silica derivatives such as silicates, silicon hydroxides and silicon oxides; plastic powder; and their mixtures. 3037337 33
    [0006]
    A solid bitumen according to any one of the preceding claims, wherein the coating layer comprises at least 10% by weight of an anti-caking compound with respect to the total weight of the coating layer, preferably from 10 to 90 % by weight, more preferably from 15 to 90% by weight.
    [0007]
    7. Solid bitumen according to any one of the preceding claims, wherein the bitumen base has a needle penetration measured at 25 ° C according to EN 1426 from 5 to 330 1/10 mm, preferably from 20 to 220 1/10 mm. . 10
    [0008]
    8. Solid bitumen according to any one of the preceding claims, wherein the bitumen base further comprises at least one chemical additive selected from: an organic compound, a paraffin, a polyphosphoric acid and mixtures thereof. 15
    [0009]
    9. Solid bitumen according to any one of the preceding claims, wherein the bitumen base has a penetrability of 5 to 45 1 / 10mm, measured at 25 ° C according to EN 1426 and / or a ball and ring softening temperature upper or equal to 90 ° C, the ball and ring softening temperature being measured according to EN 1427 standard.
    [0010]
    10. A process for producing a solid bitumen at room temperature in the form of granules composed of a core and a core coating layer, said process comprising: ii) shaping the core from at least a bitumen base, ii) coating the core on all or part of its surface with a composition comprising at least one viscosifying compound and at least one anti-caking compound, iii) optionally, drying the granules obtained in step ii) at a temperature ranging from 20 to 60 ° C, for a time ranging from 5 minutes to 5 hours, preferably from 5 minutes to 2 hours. 30
    [0011]
    11. solid bitumen at room temperature according to any one of claims 1 to 9 obtainable by carrying out the method according to claim 10. 3037337 34
    [0012]
    An ambient temperature solid bitumen according to any one of claims 1 to 9 and 11 which exhibits transport and storage stability at a temperature of from 20 to 80 ° C for a period of time greater than or equal to 2 months, preference greater than or equal to 3 months. 5
    [0013]
    13. Use of solid bitumen according to any one of claims 1 to 9, 11 or 12 as road binder.
    [0014]
    14. Use according to claim 13 for the manufacture of asphalt. 10
    [0015]
    15. A method of manufacturing asphalt comprising at least one road binder and aggregates, the road binder being selected from bitumens according to any one of claims 1 to 9, 11 or 12, 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 vessel such as a kneader or a kneading drum; - Obtaining mixes.
    [0016]
    16. The method of claim 15 which does not include a step of heating the road binder prior to mixing with the aggregates.
    [0017]
    17. A method for transporting and / or storing road bitumen, said road bitumen being transported and / or stored as solid bitumen at ambient temperature according to any one of claims 1 to 9 and 11 or 12. 25
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    同族专利:
    公开号 | 公开日
    EP3307830B1|2020-03-18|
    CN107709466A|2018-02-16|
    FR3037337B1|2019-06-14|
    US20180155629A1|2018-06-07|
    CN107709466B|2020-06-26|
    ZA201708338B|2018-11-28|
    EP3307830A1|2018-04-18|
    WO2016198782A1|2016-12-15|
    PL3307830T3|2020-11-02|
    CA2988469A1|2016-12-15|
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    法律状态:
    2016-05-24| PLFP| Fee payment|Year of fee payment: 2 |
    2016-12-16| PLSC| Search report ready|Effective date: 20161216 |
    2017-05-23| PLFP| Fee payment|Year of fee payment: 3 |
    2018-05-25| PLFP| Fee payment|Year of fee payment: 4 |
    2020-05-20| PLFP| Fee payment|Year of fee payment: 6 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1555261|2015-06-09|
    FR1555261A|FR3037337B1|2015-06-09|2015-06-09|SOLID BITUMEN AT AMBIENT TEMPERATURE|FR1555261A| FR3037337B1|2015-06-09|2015-06-09|SOLID BITUMEN AT AMBIENT TEMPERATURE|
    PL16734423T| PL3307830T3|2015-06-09|2016-06-07|Bitumen that is solid at ambient temperature|
    PCT/FR2016/051360| WO2016198782A1|2015-06-09|2016-06-07|Bitumen that is solid at ambient temperature|
    EP16734423.3A| EP3307830B1|2015-06-09|2016-06-07|Bitumen that is solid at ambient temperature|
    CN201680034140.8A| CN107709466B|2015-06-09|2016-06-07|Bitumen that is solid at ambient temperature|
    US15/735,473| US20180155629A1|2015-06-09|2016-06-07|Bitumen that is solid at ambient temperature|
    CA2988469A| CA2988469A1|2015-06-09|2016-06-07|Bitumen that is solid at ambient temperature|
    ZA2017/08338A| ZA201708338B|2015-06-09|2017-12-08|Bitumen that is solid at ambient temperature|
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