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    • 专利摘要:
    The present invention relates to a method for transporting and / or storing cold road bitumen, said bitumen being transported and / or stored in the form of bitumen cake and comprising at least one chemical additive chosen from: • a compound of general formula ( I): R1- (COOH) z in which R1 is a linear or branched, saturated or unsaturated hydrocarbon-based chain comprising from 4 to 68 carbon atoms, preferably from 4 to 54 carbon atoms, more preferably from 4 to 36 atoms carbon number and z an integer ranging from 1 to 4, preferably from 2 to 4, and • a compound of general formula (II): R- (NH) nCONH- (X) m -NHCO (NH) nR 'in which R and R ', which may be identical or different, contain a saturated or unsaturated, linear or branched, cyclic or acyclic hydrocarbon-based chain containing from 1 to 22 carbon atoms and optionally comprising hetero atoms and / or rings having from 3 to 12 atoms and / or heterocycles having from 3 to 12 carbon; X contains a hydrocarbon chain, saturated or unsaturated, linear or branched, cyclic or acyclic, having from 1 to 22 carbon atoms and optionally comprising one or more heteroatoms and / or rings having from 3 to 12 atoms and / or heterocycles having from 3 to 12 atoms; n and m are integers having, independently of one another, a value of 0 or 1. The present invention also relates to the use of bitumen bread according to the invention as a road binder as well as their use for manufacturing asphalt.
    公开号:FR3024454A1
    申请号:FR1457537
    申请日:2014-08-01
    公开日:2016-02-05
    发明作者:Regis Vincent；Laurence Lapalu；Mouhamad Mouazen
    申请人:Total Marketing Services SA；
    IPC主号:
    专利说明:

    [0001] TECHNICAL FIELD The present invention relates to a method for transporting and / or storing a road bitumen. The present invention also relates to the use of bitumen bread according to the invention as road binder and their use for the manufacture of asphalt. 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 bitumen may become viscous 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 temperature of the bitumen for a given period may affect the properties of the bitumen, including the aging properties and thus change the final performance of the mix. To overcome the problems of transport and storage of hot bitumen, cold storage and transport solutions have been developed. This mode of transportation of cold-packaged bitumen represents only a small fraction of the quantities transported worldwide, but it corresponds to very real needs for geographical regions of difficult and expensive access by traditional means of transport.
    [0002] By way of example, mention may be made of the transport of bitumen at ambient temperature in metal drums. This means is increasingly questionable from an environmental point of view because the cold bitumen stored in the barrels must be reheated before use as a road binder. 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 cold bitumen 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 handling and transporting bituminous products in these drums, they may be difficult and dangerous if specialized drum handling equipment is not available at the carriers or where the bitumen is used. The packaging of bituminous products in paper or thermoplastic bags, such as polypropylene or polyethylene, has been the subject of recent developments. For example, the US patent application 2011/0290695 describes a system for dispensing and packaging bituminous products in block form. Each block of bitumen is surrounded by a film of bituminous composition consisting of about 10 to 30% by weight of natural bitumen and about 5 to 25% by weight of a synthetic elastomer and copolymers. The bituminous composition film is melted with the bituminous product and is fully compatible with the molten bitumen. However, it has been found that bituminous products packaged in the form of paper bags or of thermoplastic material can flow during handling, storage and transport, because the bags can be pierced increasing the risk of deformation and leakage, especially when the temperature outdoor is high. When the bags are pierced, the bitumen flows and the bags stick together. The handling of the bags thus deteriorated becomes impossible, which renders them unusable.
    [0003] Despite the recent development of bituminous product packaging, there is still a need to find a storage solution and transport of road bitumen and cold bituminous materials to overcome the drawbacks mentioned above.
    [0004] In particular, the object of the present invention is to provide an improved method of transport and / or cold storage. Another object of the invention is to provide a method for easy handling of road bitumen during handling operations.
    [0005] Another objective of the invention is to propose an ecological and economical process for transporting road bitumen and to avoid the use of additional means for maintaining the temperature of said bitumen during transport and / or storage.
    [0006] Another object of the invention is to provide an ecological process for minimizing the presence of waste and / or residues. OBJECT OF THE INVENTION The object of the invention relates to a method for transporting and / or storing cold road bitumen, said bitumen being transported and / or stored in the form of bitumen cake and comprising at least one chemical additive selected among: a compound of general formula (I): R 1 - (COOH), in which R 1 is a linear or branched, saturated or unsaturated hydrocarbon-based chain containing from 4 to 68 carbon atoms, preferably from 4 to 54 carbon atoms, carbon, more preferably from 4 to 36 carbon atoms and z an integer ranging from 1 to 4, preferably from 2 to 4, and - a compound of general formula (II): R- (NH) .CONH- (X) In which: R and R ', which may be identical or different, contain a linear or branched, cyclic or acyclic, saturated or unsaturated hydrocarbon-based chain containing from 1 to 22 carbon atoms, and optionally comprising hetero atoms and / or rings having from 3 to 12 atoms and / or heterocycles having from 3 to 12 atoms; X contains a hydrocarbon chain, saturated or unsaturated, linear or branched, cyclic or acyclic, having from 1 to 22 carbon atoms and optionally comprising one or more heteroatoms and / or rings having from 3 to 12 atoms and / or heterocycles having from 3 to 12 atoms; n and m are integers independently of one another having a value of 0 or 1.
    [0007] The term "road bitumen" is understood to mean bituminous compositions consisting of one or more bitumen bases and comprising one or more chemical additives, said compositions being intended for a road application.
    [0008] According to a particular embodiment, the road bitumen is transported and / or stored at a temperature below 100 ° C. In particular, the transport and / or storage temperature corresponds to the ambient temperature. By ambient temperature is meant the temperature which is reached during the transport and / or storage of the bitumen according to the invention without said bitumen being heated by any type of process. Thus, the ambient temperature can reach high temperatures, below 100 ° C during summer periods, especially in geographical regions with hot climate. According to a particular preferred embodiment, the bitumen is transported and / or stored at a temperature between 20 ° C and 90 ° C, preferably between 20 ° C and 80 ° C, more preferably between 40 ° C and 80 ° C. ° C, more preferably between 50 ° C and 70 ° C, more preferably between 40 ° C and 60 ° C. According to one particular embodiment, the chemical additive is a compound of general formula (I): R 1 - (COOH), in which R 1 is a linear or branched, saturated or unsaturated hydrocarbon-based chain containing from 4 to 68 carbon atoms preferably from 4 to 54 carbon atoms, more preferably from 4 to 36 carbon atoms and z an integer ranging from 1 to 4, preferably from 2 to 4.
    [0009] According to a particular preferred embodiment, the compound is a diacid of general formula HOOC-C'i12-COOH in which w is an integer ranging from 4 to 22, preferably from 4 to 12. Advantageously, the compound is a diacid selected from the group consisting of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, 1,2-dodecanedioic acid and tetradecanedioic acid . According to a particular embodiment, the chemical additive is a compound of general formula (II): ## STR5 ## , which may be identical or different, contain a linear or branched, cyclic or acyclic, saturated or unsaturated hydrocarbon-based chain containing from 1 to 22 carbon atoms and optionally comprising hetero atoms and / or rings having from 3 to 12 atoms and / or heterocycles having from 3 to 12 atoms; X contains a hydrocarbon chain, saturated or unsaturated, linear or branched, cyclic or acyclic, having from 1 to 22 carbon atoms and optionally comprising one or more heteroatoms and / or rings having from 3 to 12 atoms and / or heterocycles having from 3 to 12 atoms; n and m are integers independently of one another having a value of 0 or 1. According to a particular preferred embodiment, the compound comprises a hydrazide unit when n and m have a value of 0.
    [0010] Advantageously, the groups R and / or R ', which may be identical or different, comprise one or more aromatic mono- or polycyclic aromatic rings or heterocycles optionally substituted with one or more hydroxyl functions and / or one or more linear or branched saturated hydrocarbon chains having from 1 to 6 carbon atoms.
    [0011] According to a particular preferred embodiment, the compound comprises two amide units when n has a value of 0 and has a value of 1. According to a particular preferred embodiment, the groups R and / or R ', which are identical or different, comprise a aliphatic hydrocarbon chain of 4 to 22 carbon atoms, especially chosen from C4H9, C5H11, CH CH CH, -ii-23, -12-25, C17H35, C18H37, C21H43, C22H45 groups. Advantageously, the X group comprises an aliphatic hydrocarbon chain of 1 to 2 carbon atoms. According to one particular embodiment, the road bitumen comprises from 0.1% to 5% by weight, preferably from 0.5% to 4% by weight, more preferably from 0.5% to 2.5% by weight. of the chemical additive with respect to the total mass of said bitumen. According to another particular embodiment, the road bitumen comprises between 0.05% and 15% by weight, preferably between 0.1% and 10% by weight, more preferably between 0.5% and 6% by weight. an olefinic polymer adjuvant.
    [0012] The object of the invention also relates to the use of bitumen bread as a road binder, said bitumen bar consisting of road bitumen as described in the process according to the invention.
    [0013] According to a particular embodiment, the bitumen roll is used for the manufacture of asphalt, said bitumen bit consisting of road bitumen as described in the process according to the invention. DETAILED DESCRIPTION According to one particular embodiment, a road bitumen is prepared by bringing into contact: a bitumen base, between 0.1% and 5% by mass, preferably between 0.5% and 4% by mass, more preferably between 0.5% and 2.5% by weight of a chemical additive.
    [0014] In the remainder of the description, the mass percentages are calculated with respect to the total mass of the bitumen. It is carried out at manufacturing 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 ° C. 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 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.
    [0015] 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 mixture of bitumen bases derived from the refining of crude oil, in particular bitumen bases containing asphaltenes. 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. 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. The bitumen bases according to the invention have a penetrability, measured at 25 ° C. according to the EN 1426 standard, between 5 and 300 1/10 mm, preferably between 10 and 100 1/10 mm, more preferably between 30 and 100 1 / 10 mm. According to a particular embodiment, the chemical additive may be a compound of the following general formula (I): R 1 - (COOH), in which R 1 is a linear or branched, saturated or unsaturated hydrocarbon-based chain comprising from 4 to 68 atoms carbon, preferably from 4 to 54 carbon atoms, more preferably from 4 to 36 carbon atoms and z an integer ranging from 1 to 4, preferably from 2 to 4, more preferably equal to 2. The chemical additives corresponding to the formula (I) may advantageously be monoacids (z = 1), diacids (z = 2), triacids (z = 3) or tetracides (z = 4). The preferred chemical additives are diacids with z = 2. Similarly, the group R 1 is preferably a linear and saturated hydrocarbon chain of formula CwH 2 w with w an integer ranging from 4 to 22, preferably from 4 to 12. In particular, the chemical additives have the general formula HOOC-CwEl2w-COOH where w is an integer ranging from 4 to 22, preferably from 4 to 12. These chemical additives correspond to the preceding formula (I) in which z = 2 and Ri = CwH2w. The preferred diacids are: - adipic acid or 1,6-hexanedioic acid with w = 4 - pimelic acid or 1,7-heptanedioic acid with w = 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 - acid 1,2-dodecanedioic acid with w = 10 - tetradecanedioic acid with w = 12.
    [0016] 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 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, especially of C8 to C34, in particular 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.
    [0017] According to another particular embodiment, the chemical additive may be a compound of the following general formula (II): ## STR5 ## R ', which may be identical or different, contain a saturated or unsaturated, linear or branched, cyclic or acyclic hydrocarbon-based chain containing from 1 to 22 carbon atoms and optionally comprising hetero atoms and / or rings having from 3 to 12 atoms and / or heterocycles having from 3 to 12 atoms; X contains a hydrocarbon chain, saturated or unsaturated, linear or branched, cyclic or acyclic, having from 1 to 22 carbon atoms and optionally comprising one or more heteroatoms and / or rings having from 3 to 12 atoms and / or heterocycles having from 3 to 12 atoms; n and m are integers independently of one another having a value of 0 or 1.
    [0018] According to a variant of the invention, the integer a has a value of 0. In this particular case, the groups R- (NH) .CONH and NHCO (NH) .- R 'are covalently linked by a hydrazide bond CONH -NHCO-. The groups R and / or R ', which are identical or different, then comprise 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 condensed polycyclic system. aliphatic, partially aromatic or wholly aromatic, each ring comprising 5 or 6 atoms, taken alone or as a mixture. Preferably, the groups R and / or R ', which are identical or different, are linear, saturated hydrocarbon chains comprising from 4 to 22 carbon atoms. Among the preferred saturated, linear hydrocarbon-based chains, mention may be made of the groups C 4 H 9, C 9 H 19, CH H 23, C 16 H 25, C 17 H 35, Cl 8 H 37, C 21 H 43, C 22 H 45. According to another variant of the invention, the integer ma has a value of 1. The group R, the group R 'and / or the group X, then comprise a group chosen from at least one hydrocarbon chain of at least 4 atoms. of carbon, 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. 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, C3E16. The X group may also be a cyclohexyl group or a phenyl group, the radicals R- (NH) .CONH- and NHCO (NH) .- R'- may then be in the 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 by groups other than the two main groups R- (NH) .CONH- and -NHCO (NH) .- R '. The group X may also comprise two or more fused aliphatic and / or aromatic rings or not. Thus, according to a preferred variant of the invention, the group X is a group comprising two aliphatic rings connected by an optionally substituted CH2 group, for example: According to another variant of the invention, the group X is a group comprising two rings aromatic compounds connected by an optionally substituted CH.sub.2 group as for example: Other particular compounds are the urea derivatives, including a particular urea 4,4'-bis (dodecylaminocarbonylamino) diphenylmethane which has the formula: C12H25-NHCONH-C6H4-CH2 -C6H4-NHCONH-C12H25.
    [0019] According to a particular preferred embodiment, the chemical additive is a compound of general formula (II) in which the integer has a value of 0. Among the preferred compounds according to the invention, mention may be made of the hydrazide derivatives corresponding to the formulas C5H11-CONH-NHCO-05H11 C9H19 -CONH-NHC 0 -C9H19 C11H23-CONH-NHCO-C11H23 C 17E135-C ONH-NHC 0 -C17E135 C21H43-CONH-NHCO-C21H43.
    [0020] There may also be mentioned diamides, of which a preferred diamide is N, N'-ethylenedi (stearamide), C17H35-CONH-CH2-CH2-NHCO-C17H35. According to a particular embodiment, the road bitumen comprises from 0.1% to 5% by weight, preferably from 0.5% to 4% by weight, more preferably from 0.5% to 2.5% by weight of the chemical additive with respect to the total mass of said bitumen. According to another particular embodiment, a road bitumen is prepared by contacting: a bitumen base, between 0.1% and 5% by mass, preferably between 0.5% and 4% by mass, more preferably between 0.5% and 2.5% by weight of a chemical additive, and between 0.05% and 15% by weight, preferably between 0.1% and 10% by weight, more preferably between 0.5% by weight. % and 6% by weight of an olefinic polymer adjuvant.
    [0021] The bitumen base and the chemical additive are as described above. 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 monomer A is chosen from vinyl acetate and C1-C6 alkyl acrylates or methacrylates. Monomer B is selected from glycidyl acrylate and glycidyl methacrylate.
    [0022] 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 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 sequential copolymers, preferably random copolymers of ethylene and vinyl acetate, and statistical or block copolymers, preferably statistical copolymers. , 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.
    [0023] The olefinic polymer builder is preferably selected from the (b) ethylene / monomer A / monomer B terpolymers described above.
    [0024] Advantageously, the olefinic polymer adjuvant is chosen from the random terpolymers of ethylene, 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 a particular embodiment, the bitumen 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 with respect to the total mass of said bitumen. The amounts of the chemical additive and, optionally, the olefinic polymer adjuvant are adjusted according to the nature of the bitumen base used. In particular, the desired penetrability is preferably between 20 and 45 1 / 10mm and the target ball and ring softening temperature (TBA) is preferably greater than 90 ° C, with the understanding that penetrability is measured at 25 ° C. ° C according to EN 1426 and TBA according to EN 1427. According to a particular preferred embodiment, the road bitumen comprises a combination of the chemical additive of formula (II) and the olefinic polymer adjuvant described above. above. We prefer the combination in which the chemical additive has a formula (II) where m = 0, more preferably where m = 0 and n = 0. The combination in which the olefin polymer adjuvant is selected from the above-described (b) ethylene / monomer A / monomer B terpolymers 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 road bitumen as described above may also contain other known additives or other known bitumen elastomers such as SB copolymers (block copolymer of styrene and butadiene), SBS (styrene-butadiene block copolymer) -styrene), SIS (styrene-isoprene-styrene), SBS * (styrene-butadiene-styrene star 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 permitting crosslinking without a crosslinking agent as described in documents WO2007 / 058994, WO2008 / 137394 and by the applicant in the patent application WO2011 / 013073. According to a particular embodiment, the road bitumen consists solely of one or more bitumen bases and one or more chemical additives as described above. The object of the invention relates to a method for transporting and / or storing a cold road bitumen, said bitumen being transported and / or stored in the form of bitumen roll. The bitumen is as described above.
    [0025] By transport and / or cold storage is meant transport and / or storage at a temperature below 100 ° C, preferably at an ambient temperature below 100 ° C. The temperature is preferably between 20 ° C and 90 ° C, preferably between 20 ° C and 80 ° C, more preferably between 40 ° C and 80 ° C, more preferably between 50 ° C and 70 ° C, more preferably between 40 ° C and 60 ° C. Bitumen bit means a block of road bitumen having a mass of between 1 kg and 1000 kg, preferably between 1 kg and 200 kg, more preferably between 1 kg and 50 kg, still more preferably between 5 kg and 25 kg. kg, more preferably between 10 kg and 30 kg, said block being advantageously parallelepipedic, preferably being a block. The bitumen roll preferably has a volume of between 1000 cm3 and 50000 cm3, preferably between 5000 cm3 and 25000 cm3, more preferably between 10000 cm3 and 30000 cm3, even more preferably between 14000 cm3 and 25000 cm3. When the bitumen roll is handled manually by a person, the mass of bitumen bread can vary from 1 to 20 kg, and from 20 to 50 kg in the case of handling by two people. When handling is carried out by mechanical equipment, the mass of bitumen bread can vary from 50 to 1000 kg.
    [0026] Bitumen bread is made from road bitumen as described above according to any known method, for example according to the manufacturing method described in document US2011 / 0290695. The bitumen roll is advantageously packaged with a hot-melt film according to any known method, preferably with a polypropylene film, polyethylene film or a mixture of polyethylene and polypropylene. The bitumen packaged in bitumen roll packaged with a hot-melt film has the advantage of being ready for use, that is to say that it can be directly heated in the melter without prior unpacking or possibly introduced directly into the melter. asphalt paving plant. The hot melt material melting with the bitumen does not affect the properties of said bitumen. Bitumen bread may also be packaged in a carton according to any known method. In particular, the bitumen cake is packaged in a carton by hot casting the bitumen in a carton whose wall of the inner face is silicone and then cooled, the dimensions of the carton being adapted to the weight and / or volume of the bitumen bread desired. The object of the invention also relates to the use of bitumen bread as described above as a road binder. The road binder can in turn be used to manufacture asphalt mixes, in combination with aggregates according to any known method. 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 an asphalt binder and road aggregate having particular properties, such as anti-rutting layers, draining asphalts, or asphalts (mixing between a binder and sand-like aggregates). The bitumen rolls according to the present invention are remarkable in that they allow the transport and / or the storage of cold road bitumen under optimal conditions, in particular without creep of said loaves during their transport and / or storage, even when the ambient temperature is high and without degrading the properties of said road bitumen for road application, or even improving them.
    [0027] Examples The invention is illustrated by the following non-limiting examples. The rheological and mechanical characteristics of the bitumens referred to in these examples are measured as shown in Table 1. Table 1 Property Abbreviation Unit Measurement Standard Penetration to the needle at 25 ° C P25 1/1 0 mm NF EN 1426 Ring and ball softening temperature TBA ° C EN 1427 Viscosity Cylinder il Pa.s NF EN 13702 Bitumen BtA1, lh, 1134 Different bitumens B1, B2, B3 and B4 are prepared from the following products: - a 35/50 bitumen base, Bo, having a penetration P25 of 34 1/10 mm and a TBA of 54.4 ° C and commercially available from the TOTAL group under the AZALT® brand; a styrene / butadiene diblock copolymer, denoted SB, having a mass by weight of styrene of 30% relative to the weight of the copolymer, marketed by KRATON under the name D1184 A; a Fischer-Tropsch wax commercially available from SASOL under the trademark Sasobit °; sebacic acid; a chemical additive, 2 ', 3-bis [[343,5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide, denoted hydrazide. The mass percentages used for each bitumen are shown in Table 2 below.
    [0028] Table 2 Bitumen B1 B2 B3 B4 (control) (control) Base bitumen Bo 95% 96,5% 98,6% 99,15% SB 5% - - - Sasobit ° - 3,5% - - Sebacic acid - - 1 , 4% - Hydrazide - - - 0.85% P25 (1/1 0 mm) 27 28 25 29 TBA (° C) 95 86 109 106 The amount of additives for each bitumen is adjusted to obtain bitumens having equivalent mechanical properties, in particular near P25 penetrability and TBA. The bitumens are prepared in the following manner. For the bitumen B1, the bitumen base Bo and the copolymer SB 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. For bitumen B2, the bitumen base Bo is introduced into a reactor maintained at 165 ° C. with stirring at 300 rpm. The Fischer-Tropsch wax is then introduced into the reactor. The contents of the reactor are maintained at 165 ° C. with stirring at 300 rpm for 1 hour. Preparations of bitumens B3 and B4 are carried out by first introducing the bitumen base Bo into a reactor at 160 ° C. with stirring at 300 rpm. Then, sebacic acid (B3) or hydrazide (B4) is added in the form of granules. The mixtures are stirred for about 1 hour at 160 ° C to obtain a homogeneous final appearance. The mixtures are cooled to ambient temperature. Study of the aging properties of bitumens I30 and B3 The aging of Bo and B3 bitumens was studied according to the following protocol: Bo and B3 undergo a first aging according to the RTFOT (Rolling Thin Film Oven) method. Test) as described in standard NF EN 12607-1 and then subjected to a second test based on the principle of the PAV (Pressure Aging Vessel) test as described in ASTM D6521. The aging resistance properties of the Bo and B3 bitumens measured according to the standards mentioned above are given in the following Table 3: Table 3 Bitumen Bo B3 P25 (1/10 mm) 34 Viscosity Cylinder (Pa s) to: - 120 ° C 1,940 1,965 - 130 ° C 1,030 0,991 - 140 ° C 0,620 0,535 - 150 ° C 0,375 0,360 - 160 ° C 0,224 0,230 After aging RTFOT P25 (1/10 mm) 25 21 Viscosity Cylinder (Pa s) to : - 120 ° C 3,140 3,279 - 130 ° C 1,610 1,621 - 140 ° C 0,898 0,942 - 150 ° C 0,537 0,564 - 160 ° C 0,343 0,352 After aging RTFOT and PAV P25 (1/10 mm) 18 19 Isomodulation temperature at 300 MPa (° C) -12.6 -13.0 Slope at isomodule temperature at 300 MPa 0.273 0.266 Critical temperature (m = 0.300) (° C) -8.5 -8.4 Bitumen B3 has aging resistance properties equivalent to the bitumen base Bo without additive. The viscosity values of the bitumen B3 remain almost identical to those of the bitumen base Bo. The workability of hot bitumen B3 therefore remains unchanged with respect to the bitumen base Bo.
    [0029] Moreover, the properties of the bitumen B3 according to the invention are not affected after aging RTFOT. The RTFOT test shows that the penetrability decreases less in the bitumen B3 than in the starting bitumen base Bo, after simulated aging.
    [0030] Thus, the addition of sebacic acid to the bitumen base Bo makes it possible to obtain a binder having the necessary specifications for a road application. Presence of Bitumen P1 P2 P3 and P4 P1 to P4 bituminous bars are prepared from bitumen B1 to B4 respectively according to the following method. A mass of about 0.5 kg of bitumen is cast at 160 ° C in a rectangular steel mold covered with a polyethylene hot melt film. The mold is then cooled to room temperature and then demolded.
    [0031] Creep test A qualitative creep test is carried out beforehand. The bitumen rolls Pi, P2, P3 and P4 thus obtained are placed in incubators at different temperatures and under a load of 2.5 kg (+/- 50 g) to simulate the stacking of the loaves on each other, during transport and / or storage. Indeed, it is estimated that 6 loaves are stacked vertically on a pallet during the transport and / or storage of bitumen bars. The blocks are first placed in an oven at a temperature of 40 ° C. If no creep is observed after a certain time, at most after 3 weeks, new loaves are molded and placed at an oven temperature of 50 ° C for at least 7 days. This operation is repeated by increasing the temperature from 10 ° C to a maximum temperature of 80 ° C if no creep is observed, or up to the temperature where a large creep breads is observed if said temperature is below 80 ° C. Creep results visually in deformation of the loaves and flow of the bitumen.
    [0032] Table 4 below lists the results of the creep test obtained for the various bitumen bars.
    [0033] Table 4 Bitumen loam Pi P2 P3 P4 (control) (control) Oven temperature (° C) 40 + + +++ +++ 50 - - +++ +++ 60 np * np * +++ +++ 70 np * np * +++ +++ 80 np * np * ++ ++ +++: no creep observed after 15 days ++: no creep observed after 7 days +: slight creep observed after 3 days -: significant creep in less than 2 hours * np: irrelevant; the creep test was not performed at this temperature since creep is observed at lower temperatures.
    [0034] Only bitumen bars P3 and P4 according to the present invention do not flow under conventional storage and / or transport conditions. Creep Resistance Test This test is carried out in order to evaluate the deformation resistance of each bit of bitumen P1, P2, P3 and P4 when it is subjected to a load and at a temperature of 50 ° C. The creep resistance test itself 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 cylindrical metal box containing a mass of 60 g of bitumen cake is placed inside the thermal enclosure set at a temperature of 50 ° C. 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 surface of the bitumen cake. Then, it moves vertically downwards, at a constant speed of 1 mm / min, over a calibrated distance of 10 mm so as to exert a compressive force on the upper surface of the bitumen roll. The texture analyzer measures the maximum compressive force applied by the piston to the bitumen roll at 50 ° C. The measurement of the maximum compressive strength makes it possible to evaluate the ability of the bitumen roll to resist deformation. Thus, the greater this strength, the better the resistance to deformation of the bitumen bread.
    [0035] The results are listed in Table 5 below. Table 5 Asphalt bit P1 P2 P3 P4 (control) (control) Maximum compression force (N) 3.95 4.40 26.96 110.84 Although the values of the penetrability pair P25 and TBA of the P1 bitumen rolls to P4 are equivalent, the latter behave differently to deformation. Indeed, it is estimated that a bitumen cake is sufficiently resistant to creep when the maximum compressive force is at least 25 N at 50 ° C. Thus, the breads P3 and P4 according to the invention are particularly resistant to creep compared to control bitumen breads Pi and P2. In addition, the bread P4 containing the hydrazide is remarkable insofar as the maximum compressive force is approximately 25 times greater than that applied to control bituminous breads P1 or P2 which will tend to flow during their transport or their storage, especially at temperatures greater than or equal to 40 ° C, preferably greater than or equal to 50 ° C, more preferably greater than or equal to 60 ° C.
    [0036] Thus, the bitumen rolls according to the invention do not stick to each other and keep their shape and consistency even at high ambient temperature. Thus, transport and / or storage are optimized for the bitumen rolls according to the invention, with facilitated handling, secure and minimized bitumen losses.
    [0037] Study of the properties of bituminous mixes Et) and E3 Asphalt mixes E0 and E3 were prepared respectively from bitumens Bo and B3. The mixes E0 and E3 comprise respectively 5.4% by weight of bitumen Bo or B3 and 94.6% by weight of aggregates, said percentages being calculated relative to the weight of the bituminous mix.
    [0038] The mixes are prepared by mixing bitumens and aggregates at 165 ° C according to a conventional method. The properties of the mixes E0 and E3 measured above are given in Table 6 below: Table 6 Coated Et) E3 Duriez Test (1) Void content (%) 10.30 9.80 r (MPa) 8.7 10 , 9 R (MPa) 10.5 12.8 r / R (%) 83 85.3 Rutting (2) Void content (%) 6.6 6.8 Rut depth at 30000 cycles (%) 3, 5 3.6 Low Temperature Cracking (TSRST) (3) Cracking Temperature (° C) -24.6 -23.0 Cracking Stress (MPa) 4.38 4.20 (1) Stripping Resistance Test to water according to standard NF EN 12697-12 (method B) (2) Rutting resistance test according to the standard NF EN 12697-22 (3) Cracking test at low temperature according to standard NF EN 12697- Asphalt mixes made with bitumen according to the invention as road binder have identical properties compared to a mix of the prior art Et). The addition of one or more additives according to the invention in a bitumen does not affect the properties of the mixes made from such bitumen.
    [0039] Thus, for each test carried out, the void contents are comparable for E0 and E3, which indicates equivalent workability. This observation is consistent since the Bo and B3 bitumens have comparable viscosities between 120 ° C and 160 ° C (see Table 3). In addition, the resistance values r and R are higher for the mix E3 than for the mix Eo. The modulus and fatigue properties of the E3 mix are very satisfactory compared to the Eo mix.
    权利要求:
    Claims (16)
    [0001]
    REVENDICATIONS1. A method for transporting and / or storing cold road bitumen, said bitumen being transported and / or stored in the form of bitumen cake and comprising at least one chemical additive chosen from: a compound of general formula (I): R1- (COOH) in which R 1 is a linear or branched, saturated or unsaturated hydrocarbon-based 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 integer ranging from 1 to 4, preferably from 2 to 4, and - a compound of general formula (II): R- (NH) .CONH- (X) ', - NHCO (NH) .- R' wherein: R and R ', which are identical or different, contain a saturated or unsaturated, linear or branched, cyclic or acyclic hydrocarbon-based chain containing from 1 to 22 carbon atoms and optionally comprising hetero atoms and / or rings having from 3 to 12; atoms and / or heterocycles having from 3 to 12 atoms; X contains a hydrocarbon chain, saturated or unsaturated, linear or branched, cyclic or acyclic, having from 1 to 22 carbon atoms and optionally comprising one or more heteroatoms and / or rings having from 3 to 12 atoms and / or heterocycles having from 3 to 12 atoms; n and m are integers independently of one another having a value of 0 or 1. 25
    [0002]
    The method of claim 1, wherein said road bitumen is transported and / or stored at a temperature below 100 ° C, preferably at an ambient temperature below 100 ° C. 30
    [0003]
    3. Method according to one of claims 1 and 2, wherein said road bitumen is transported and / or stored at a temperature between 20 ° C and 90 ° C, preferably between 20 ° C and 80 ° C, plus preferably between 40 ° C and 80 ° C, more preferably between 50 ° C and 70 ° C, more preferably between 40 ° C and 60 ° C.
    [0004]
    4. Process according to any one of claims 1 to 3, in which the chemical additive is a compound of general formula (I): R 1 - (COOH), in which R 1 is a linear or branched hydrocarbon-based chain, saturated or unsaturated compound comprising from 4 to 68 carbon atoms, preferably from 4 to 54 carbon atoms, more preferably from 4 to 36 carbon atoms and z an integer ranging from 1 to 4, preferably from 2 to 4.
    [0005]
    5. The process according to claim 4, wherein said compound is a diacid of the general formula HOOC-C, E12, -COOH wherein w is an integer ranging from 4 to 22, preferably from 4 to 12.
    [0006]
    6. Method according to one of claims 4 and 5, wherein said compound is a diacid selected from the group consisting of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid , undecanedioic acid, 1,2-dodecanedioic acid and tetradecanedioic acid.
    [0007]
    7. Process according to any one of claims 1 to 3, wherein the chemical additive is a compound of general formula (II): R- (NH) .CONH- (X) ', - NHCO (NH) .- R 'in which: R and R', which may be identical or different, contain a saturated or unsaturated, linear or branched, cyclic or acyclic hydrocarbon-based chain containing from 1 to 22 carbon atoms and optionally comprising heteroatoms and / or rings; having from 3 to 12 atoms and / or heterocycles having from 3 to 12 atoms; X contains a hydrocarbon chain, saturated or unsaturated, linear or branched, cyclic or acyclic, having from 1 to 22 carbon atoms and optionally comprising one or more heteroatoms and / or rings having from 3 to 12 atoms and / or heterocycles having from 3 to 12 atoms; n and m are integers independently of one another having a value of 0 or 1. 30
    [0008]
    The process of claim 7, wherein said compound comprises a hydrazide moiety when n and m are 0.
    [0009]
    9. Process according to claim 8, in which said groups R and / or R ', which are identical or different, comprise one or more aromatic mono- or polycyclic rings or heterocycles optionally substituted by one or more hydroxyl functions and / or one or more chains. linear or branched saturated hydrocarbon compounds having 1 to 6 carbon atoms.
    [0010]
    The method of claim 7, wherein said compound comprises two amide units when n has a value of 0 and m has a value of 1.
    [0011]
    11. Process according to any one of claims 7 to 10, in which said R and / or R 'groups, which are identical or different, comprise an aliphatic hydrocarbon chain of 4 to 22 carbon atoms, in particular chosen from the groups C4H9 and C5Hii. C9H19, CHH23, C121-125, C17H35, C18H37, C21H43, C22H45.
    [0012]
    The process according to any one of claims 7 to 11, wherein said X moiety comprises an aliphatic hydrocarbon chain of 1 to 2 carbon atoms.
    [0013]
    13. Process according to any one of claims 1 to 12, in which the road bitumen comprises from 0.1% to 5% by weight, preferably from 0.5% to 4% by weight, more preferably from 0.5% by weight. % to 2.5% by weight of said chemical additive relative to the total mass of said bitumen.
    [0014]
    14. Process according to any one of claims 1 to 13, in which the road bitumen comprises between 0.05% and 15% by weight, preferably between 0.1% and 10% by mass, more preferably between 0.5% by weight. % and 6% by weight of an olefinic polymer adjuvant.
    [0015]
    15. Use of bitumen bars as described in any one of claims 1 to 14 as a road binder.
    [0016]
    16. Use according to claim 15 for the manufacture of asphalt.
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    同族专利:
    公开号 | 公开日
    WO2016016320A1|2016-02-04|
    MA39894B1|2018-12-31|
    EP3174926A1|2017-06-07|
    FR3024454B1|2016-08-19|
    CA2956868A1|2016-02-04|
    ZA201700726B|2020-01-29|
    US20170218177A1|2017-08-03|
    MA39894A1|2017-07-31|
    CN107075169A|2017-08-18|
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    法律状态:
    2015-07-27| PLFP| Fee payment|Year of fee payment: 2 |
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    2016-07-20| PLFP| Fee payment|Year of fee payment: 3 |
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1457537A|FR3024454B1|2014-08-01|2014-08-01|METHOD FOR TRANSPORTING AND / OR STORING ROAD BITUMEN|FR1457537A| FR3024454B1|2014-08-01|2014-08-01|METHOD FOR TRANSPORTING AND / OR STORING ROAD BITUMEN|
    MA39894A| MA39894B1|2014-08-01|2015-07-28|Method of transporting and / or storing road bitumen|
    CA2956868A| CA2956868A1|2014-08-01|2015-07-29|Method for the transportation and/or storage of road bitumen|
    PCT/EP2015/067409| WO2016016320A1|2014-08-01|2015-07-29|Method for the transportation and/or storage of road bitumen|
    EP15752943.9A| EP3174926A1|2014-08-01|2015-07-29|Method for the transportation and/or storage of road bitumen|
    CN201580046478.0A| CN107075169A|2014-08-01|2015-07-29|Method for transporting and/or storing road asphalt|
    US15/501,040| US10683421B2|2014-08-01|2015-07-29|Method for the transportation and/or storage of road bitumen|
    ZA2017/00726A| ZA201700726B|2014-08-01|2017-01-30|Method for the transportation and/or storage of road bitumen|
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