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    • 专利摘要:
    The present invention relates to bitumen granules comprising at least one chemical additive chosen from: • a compound of general formula: 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 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) nCONH- (X) m -NHCO (NH) nR '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 having 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 having, independently of each other, a value of 0 or 1. The present invention also relates to a method of transporting and / or storing cold road bitumen, said bitumen being transported and / or or stored as bitumen granules according to the invention. The present invention also relates to the use of bitumen granules according to the invention as road binder and their use for the manufacture of asphalt.
    公开号:FR3024456A1
    申请号:FR1457538
    申请日:2014-08-01
    公开日:2016-02-05
    发明作者:Sophie Mariotti；Regis Vincent
    申请人:Total Marketing Services SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to road asphalt granules. The present invention also relates to a method for transporting and / or storing cold road asphalt in the form of granules, the use of the granules according to the invention as road binder and their use for the manufacture of asphalt.
    [0002] RT 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. The delivery distances of the 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 c --sport and storage of bitumen to aud, solutions for transport and storage in cold conditioning 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 areas of access that are expensive and expensive by traditional means of transport.
    [0003] As currently used cold transport, we can mention the transport of bitumen at room 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. By way of other examples, mention may be made of bitumens in the form of granules transported in bags. These granules have the advantage of being easily manipulated. US Patent 3,026,568 discloses bitumen granules coated with a powdery material, such as limestone powder. However, the bitumen granules tend to adhere to each other and agglomerate during storage and / or transport, especially at high ambient temperatures and for long periods. There is a need to find a transportable and / or cold storable road bitumen to overcome the drawbacks of the prior art. In particular, the object of the present invention is to provide a transportable and / or storable road bitumen at high ambient temperatures, especially at a temperature below 100 ° C, preferably between 20 ° C and 90 ° C.
    [0004] Another object of the invention is to provide an easily manipulable road bitumen, especially at high ambient temperatures, particularly at a temperature below 100 ° C, preferably between 20 ° C and 90 ° C. Another object of the invention is to provide an ecological and economical method for transporting road bitumen and to avoid the use of additional means for maintaining the temperature of said bitumen during transport and / or storage. The subject of the invention relates to bitumen granules comprising at least one chemical additive chosen from: a compound of general formula (I): R - (COOH), in which R 'is a hydrocarbon-based chain , linear or branched, saturated or unsaturated 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 to 4, and a compound of general formula (II): R - (NH) CONII- (X) n - NHCO (NH) n - R 'in which: R and R', which may be identical or different, contain a hydrocarbon chain, saturated or unsaturated, linear or branched, cyclic or acyclic, having 1 to 22 carbon atoms and optionally comprising hetero atoms and / or rings having 3 to 12 atoms and / or heterocycles having 3 at 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 embodiment, the chemical additive is a compound of general formula (I): R1- (COOH) in which R '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 an integer ranging from 1 to 4, preferably from 2 to 4.
    [0005] IT. Advantageously, the compound is a diacid chosen from a group consisting of α-1Hic acid, pimelic acid, suberic acid, acid with sebacetic acid, and In a particular embodiment, the chemical is a compound of the general formula (II): in which: R and R ', which may be identical or different, contain a saturated or unsaturated, branched or cyclic or acyclic hydrocarbon-based chain containing from 1 to 22 carbon atoms, optionally comprising hetero atoms and / or rings; having 3 to 12 atoms and / or heterocycles having 3 to 12 atoms; X contains a linear or branched, cyclic or acyclic hydrocarbon chain, saturated or linear, having from 1 to 22 carbon atoms and optionally comprising one or several heteroatoms and / or rings having from 3 to 12 atoms and / or h loops having from 3 to 12 atoms mes and m are integers independently of one another having a value of 0 or 1. According to a particular preferred embodiment, a hydrazide moiety is defined when n and m are 0. 'a- a ° Advantage t - -nt, the groups R and /,,. 1, or different, include one or more substituted heterocyclic heterocycles optionally substituted with one another. several fc ... .__ s L: yle and / ot. . 1 several hydrocarbon chains - linear or branched, having from 1 to 6 carbon atoms. 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. Re, according to a particular embodiment, the bitumen granules comprise in bulk, preferably from 0.5% to 4% by weight, more preferably 0.5% - by weight of chemical additive relative to the total mass of said granules. According to a particular embodiment, the granules comprise at least one olefinic polymer adjuvant functionalized with at least glycidyl functional groups. According to a particular preferred embodiment, the olefinic polymer adjuvant is selected from the group consisting of: (a) random or block copolymers of ethylene and a monomer selected from glycidyl acrylate and methacrylate glycidyl, comprising from 50% to 99.7% by weight of ethylene; (b) terpolymers, random or sequential, of ethylene, of a monomer A selected from vinyl acetate and C1-C6 alkyl acrylates or methacrylates and a B monomer selected from acrylate of glycidyl and glycidyl methacrylate, comprising from 0.5% to 40% by weight of units derived from monomer A and from 0.5% to 15% by weight of units derived from monomer B, the remainder being formed from units from ethylene; and (c) copolymers resulting from the grafting of a monomer B selected from glycidyl acrylate and glycidyl methacrylate, onto a substrate consisting of a polymer selected from polyethylenes, polypropylenes, random or block copolymers of ethylene and vinyl acetate and the random or block copolymers of ethylene and C1-C6 alkyl acrylate or methacrylate, comprising from 40% to 99.7% by weight of ethylene, said graft copolymers comprising from 0.5% to 15% by weight of grafted units derived from the polymeric B lefin monomer is chosen from random terpolymers.
    [0006] According to a preferred embodiment, the granules comprise from 0.05% to 15% by weight, preferably from 0.1% to 10%, and more preferably from 1% to 5% by weight. mass of the olefinic polymer - mode of realization, - - - - - - - - - - - - - - - - - carbon, wood, alone or in mixture and covered on at least one of the following: (i) Panti-ag, - ° 125 1.1m, of,, cement, and powder In a particular embodiment, the anti-caking agent is talc, and the object of the invention also relates to a method for transporting and / or storing bitumen. wherein said road bitumen is transported and / or stored in the form of grits in the form of grits in the form of bitumen compositions and c-7 - or more -, if any, composites intended for a Highway.
    [0007] According to a particular embodiment, the road bitumen is transported stored at a temperature below 100 ° C., preferably at an ambient 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 - dyes during the transport and / or storage of the bitumen according to the invention without said bitu) it heated by any type (Irnced. less than 100 ° C during periods, especially in geographical regions with a hot climate.
    [0008] The invention also relates to the use of bitumen granules as road binder, said bitumen granules being such that described in a particular embodiment, the bitumen granules are used for the manufacture of bituminous mixes, said granules being as described above DESCRIPTION OF THE PREFERRED EMBODIMENTS According to a particular embodiment, the asphalt granules are prepared from road bitumen, said road bitumen being prepared by contacting one or more L base, and between 0.1% and 5%, preferably between 0.5% and 4%, preferably Between 0.5% and 2.5% by weight of a chemical additive In the remainder of the description, the mass percentages are based on the total weight of the road bitumen. - between 100 ° C and 200 ° C, preferably between 140 ° C and 200 ° C, more preferably between 140 ° C and 170 ° C, and stirring for a period of at least 10 minutes, preferably between 30 minutes and 10 hours, preferably between 1 hour and 6 months. The temperature of manufacture, the heating temperature of the bitumen base (s) before mixing and the mixing temperature are mentioned. The temperature and the duration of the heating vary according to the quantity of bitumen used and are defined by NF EN 12594. tp us mass, Among the bitumen bases that can be used according to the invention, mention may first be made of the bitumens of origin. naturally occurring natural bitumen, natural asphalt or oil sands and bitumen from crude oil refining. The bitumen bases according to the invention are advantageously chosen from bitumen bases originating from the refining of crude oil. The bitumen bases can be chosen from bitumen bases or mixture of bituminous bases derived from the refining of crude oil, in particular bitumen bases containing asphaltenes.The bitumen bases can be obtained by means of the rico-nd Refining, by distillation directly from the petrification process, is usually carried out in a viscous manner and / or phalated and / or rectified to a number of different bitumen bases obtained from the refining processes. The bitumen base can also be a bitumen base that can be recycled.The bitumen bases can be bitumen bases of hard grade or soft grade. The invention has a penetrability, measured at 25 ° C according to EN 1426, of between 5 and 0 1/10 mm, preferably between 10 and 100 1/10 mm, more preferably between 0 and 100 1/10 mm. According to one embodiment In particular, the chemical additive may be subjected to the following general formula (I): R 1 - (COOH), in which R 1 is a hydrocarbon-based chain, referred to herein as "R" or "R". saturated compound comprising from 4 to 68 carbon atoms, preferably from 4 to 5 carbon atoms, more preferably (from 1 to 4, preferably from 2 to 4, more preferably equal to 2.
    [0009] The chemical additives of formula (I) may advantageously be monoacids 1), diacids (z = 2), triacids (z = 3) or tetracides (z = 4). The preferred chemical additives are diacids with z = 2. Similarly, the R 'group is preferably a linear and saturated hydrocarbon chain of formula C, E2, with w an integer ranging from 4 to 22, preferably from 4 to 12. The chemical additives have, in particular, the general formula HOOC-CM-12w-00011 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 R 1 = C, H 2 w. Preferred diacids are: - adipic acid or hexanedioic acid - v = 4 - pimelic acid or 1,7-heptanluioïc acid, uvac w - 5: suberic acid or 1,8-octanedioic acid with w = 6: azelaic acid or 1 9-nonanedioic acid with w = 7 sebacic acid or 10-decanedioic acid with w 8 undecanedioic vacuum with w = 9 - 1,2-dodecanedioic acid (that with w = 10 - tetradecanedioic acid with w The diacids may also be dimethyl sulphates of a saturated fatty acid, for example from a unsaturated fat or from unsaturated unsaturated acids Dimer of unsaturated fatty acid (s) are chilled (by reaction of i amolecule 'me) unsaturated fatty acid (from Diels Alder by erence, it dimerises They are derived from the dimerization of an α, ins-unsaturated, especially C en to C34,, especially C₁₂ to C₂₂ n, C₁ to C₁., and C dim to C dim.-dimer. .-fat cide i '' re r is .. Linoleoic acid by dimeth, which subsequently (. Another example of this is the mother of ac, preferred to form HOOC- (CH CH = CH- (CH 2) 7). 71. Another fatty acid dimer was obtained by dimerization of the methanol linoleate. In this way, we find the triacids of a. Fatty el. In another particular embodiment, the chemical additive may be a compound of the following general formula (II): ## STR1 ## wherein: ## STR2 ## R-ONI-I- (LI-ICO (N.sub.11) '- R' in which R and R ', which are identical, contain a hydrocarbon chain, saturated or unsaturated, linear or branched, cyclic or acyclic, having from 1 to with carbon atoms and optionally comprising heteroatoms, c) -es having 3 to 12 atoms and / or heterocycles having 3 to 12 atoms; Comparing the 3 to 1, depending on the formula, the integer sorting has a value of 0. R- (NH) nCONI and NHCO (NH) -R 'are linked by: a CONH-NHCO hydrazide bond. The groups R 1 and / or ILLG 1, which are at least 4, may then comprise a group selected from at least one hydrocyclic chain, of at least 4 carbon atoms, at least one group of at least 3 to 8 atoms and at least one aliphatic polycyclic lens system. Although it was partly aromatic, each cycle consisted of 5 or 6 atoms, taken alone or as a mixture.
    [0010] Preferably, the same or different R and / or R 'groups are saturated Dnes I chains comprising from 4 to 22 carbon atoms. Preferred linear, saturated chains are C5F11 1, C91-119, C121125, C171135, C18H37, C21H43, C22t445.
    [0011] According to an ANter variant of PL, ention, the integer m has a v_ "1: 1. The groupemer". 3 to 8 atoms, at least one system pol. condensed the group R minus one chain: group X, then comprise a carbon group of at least 4 i of cari; i of a alipl partially aroma or fully aromatic cycle, each cycle comprising 5 or 6 atoms, r il or in mi) e prefer; representative, - mir> linear hydrocarbon chain, comprising from 1 to 22 carbon atoms. De -, e, the group X is selected from the groups C2H4, C3H6. The group X may also be a hexyl or a phenyl group, the radicals R- (NH) CONH- and NHCO (NH) n -R'- may then be in ortho, meta or para pos. 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 -NHCO (NH), - R'. t or aliphatic or aliphatic nat urs, whether or not. 1 rim preferred Pin., Roupement .inement I; According to another variant of the invention, the group A is a group having two groups connected by a substitution CH 2 moiety substituted as for example: Other crits, particiili, us sor-- particular the 4,42-biF idecylaminocarbonylamino) diphenylmethane which has po. C12H25-1 CONE 6H4-C1-12-C6H4-1 CCI-C is a most preferred chemical additive is a compound (II) in which the integer n theirs from 0.
    [0012] Among the compounds produced according to the invention, the hydrazide derivatives have the following formulas: ## STR2 ## NHCO-C 7 C211143-I-NHCO-C21 may also be mentioned .mides, a preferred diamide is N, 1V-ethylened (stéaram ide) C 17H35-CONH-C-H2-CH2-NHCO-C17H35 According to another particular embodiment, the granules are prepared from a road bitumen, said road bitumen being prepared by bringing into contact: one or more bi ases between 0.1% and 5% by preference 0 , 5% and 4% by weight, more preferably between 5% and 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% and 6% by weight of an olefinic polymer adjuvant The bitumen base and the chemical additive are as described above.
    [0013] 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 polymeric B-monomer. (a) The Athylene / (meth) acrylate-lycidyl copolymers are advantageously chosen from random or sequential copolymers, preferably random copolymers of ethylene and a moldy monomer from the acylate and methacrylate. The glycidyl compound has a content of 99.7%, preferably 60% to 95%, more preferably 60% to 90% by weight of ethylene. (b) The terpolymers are advantageously chosen from the random or sequential terpolymers, preferably random, of ethylene, a monomer A and a monomer B. The monomer A is chosen from vinyl and C1-C6 alkyl acrylates or methacrylates.
    [0014] The monomer B is chosen from glycidyl acrylate and glycidyl methacrylate. The ethylene / monomer A / monomer B terpolymers comprise from 0.5% to 40% by weight, preferably from 5% to 35% by weight, more preferably from 10% to 30% by weight of units derived from monomer A and from 0.5% to 15% by weight, preferably from 2.5% to 15% by weight of units derived from monomer B, the remainder being formed patterns derived from ethylene. (c) The; 1 ners result from the greilage of a monomer B chosen from the glycidyl acrylate glycidyl ester, on a 1 c substrate. The polymeric substrate consists of polyethylenes, polypropylene low density polyethylenes, randomized statistical polymers, preferably vinyl acetate and vinyl acetate, and copolymer or sequencers, styrene, ethylene glycol and acrylate or C1-C18 -lacrylate, containing 40% by weight, preferably 11% by weight of ethyl ether, 0.5% at 15 ° C to the pref of 1 '' '' '' or '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' The monomer A / B is as described above, wherein (a) and (b) is selected from the following: Of the acrylates or methacrylates C 1 -C 6 alkyl selected from the group consisting of: (a) and glycidyl, from 0.5% to 40% by weight, of from 35% to 10% by weight, more preferably from 10% to 10% by weight of the monomers obtained from the monomer, and from 0% to 15% by weight; .e from 2.5% to 1 esse of motifs from monomer B being formed from ethylene. According to a particular embodiment, 1% of the batteries comprise L of 0.05%. in bulk, preferably from 0.1% to 10% by weight, more preferably from 0.5% to 6% by weight of the olefinic polymer adjuvant in total ratio of said granules. The amounts of the chemical additive and, optionally, the olefinic polymer adjuvant are adjusted according to the nature of the bitumen base (s) used, the desired penetration of which is preferably within the range of 20 to 20%. 4. 1 / 10mm and / or the ball and r reading temperature (TBA) is preferably greater than 90 ° C, it being understood that the penetrability is measured at 25 ° C according to EN 1426 and the TBA according to the EN 1427. A specific modification of the formula (II) and chemical additive will also be preferred, in which the polymeric additive is preferably one of the monomers. B, above, and preferably includes the additive of form II) or m = (iferentiated: 0 and n = 0 and the adjuvant is added), where the terpolyine (b) ethylene / monomer is used; P Honomer With Water The road bitumen as described above may also contain other additives or other additives. For example, for coarse bitumen 3 such as coils 3 (copolymer). styrene and butadiene), SBS (styrene-butadiene block copolymer), SIS (: e-isoprene-st), SBS (styrene-butadiene-styrene star copolymer), SBR ( butyl-butadiene rubber), butylene diene nidine. The elastomers may be cross-linked, for example sulfur. There may be mentioned elastomers d; From my styrene (butane), this agent-free crosslinking agent is described in WO200 58994, the disclosure of which is incorporated in US Pat.
    [0015] According to a particular embodiment, the road surface consists of one or more bitumen bases and one or more chemical additives as described above. road bitumen as described above according to known, for example the manufacturing method described in US 3,026,568, WO 2009/13324 or WO 12/168380, in particular embodiment, the shaping of the granules can be carried out by draining, in particular by means of a drum.
    [0016] Other techniques can be used in the gram-bitumen manufacturing process, in particular molding, extrusion, etc. The granules of bitumen salt have preferably a cylindrical or spherical shape. The size of the bitumen granule is tc that the longest average dimension is preferably less than 20 mm, more preferably less than 10 mm, still more preferably lower manufacturing process - The size of the bitumen granule can vr depending on the in In a particular embodiment, the bitumen units are open on part of their surface with an anti-caking agent, preferably over their entire surface. Any compound which adhesion iules them during their transport and / or their ambient temperature ......... and ensures their fluidity during handling. The "agglomerant" is preferably neither talc, nor is it generally from inf. To 125 pm, sand, cement, wood, such as lignite powder glass of plastics material or 1-- ppa of mineral or organic origin, more preferably telange, glomeran talc.
    [0017] The anti-agglomerating layer of the novel bitumen granules is preferably at least 90% pure. The surface of the soul is covered with an anti-caking agent. preferably at least 95%, more preferably in the names 99%. The average thickness of the anti-caking layer is preferably greater than or equal to 20 μm. The layer of; The agglomerate must be sufficiently thick to be continuous. The thick film of the anti-caking layer is less than or equal to 10 t. dP asphalt glove rec_ 'green anti-agglomeran. according to any known method, for example according to the procedure described in US Pat. No. 3,026,568, the subject of the invention relates to a method of transporting and / or storing a cold road bitumen, said bitumen being transported and / or stored in the form of bitumen granules as described above.
    [0018] The transport and / or cold storage, a transport and / or a storage tank is carried out at 10 ° C, preferably at a pre-set time, as follows: between 20 ° C and 4 ° C above the average of 50 ° C and more preferably between 50 ° C and 70 ° C, and more preferably between 4 ° C and 1 ° C. Preferably, and / or stored in bulk in sizes of from 1 kg to 30 kg or 5 kg to 1000 kg commonly referred to in the field of roadside bikes of the so-called Big I bags. state of thermal material or in cartons of 5 kg to 31 or in yarns of 2.00 kg The object of the invention also relates to the use of bitumen granules as described above as binders. It is used in the manufacture of coatings, in combination with aggregates according to the known process, and in the form of bituminous mixes, which have been raised and dewatered, and asphalt properties. ilised as materials for the construction of maintenance of i. For all types of work, such as hot-rolled, cold mix- ture, linkage, other asphalt binder and road aggregates, and special anti-corrosion coatings. , asphalt mixes (melanic acid binding bit aggregates - J,) and sand).
    [0019] According to a particular mode, the die of preparation of i. i) comprises the addition of the temperature of granules as described above to aggregates in the range of from 100 ° C to 180 ° C, preferably from 100 ° C to 180 ° C, preferably from 100 ° C to 180 ° C. 160 ° C. In contact with the hot cells, the granules are melted and sufficient stirring is carried out by addition of the bit granules (maintained for at most lutes, preferably at most 1 minute to allow a homogeneous mixture. It is particularly important for the hot granulates to be melted directly prior to being melted. The granules of bitumen according to the present invention are remarkable in that they allow the transport and / or storage of cold road asphalt under optimal conditions, in particular without agglomeration and adhesion of said granules to one another during their transport and / or storage, even when the ambient temperature is high and without degrading the properties of said road bitumen for an Exe road application The Ventior.-7 .'- .-, x the examples. -nivants given - (itre non Frni * -1-if., characterist ------ i and V.,. - Y-iql.r -, - - - :: bitumen aux1-7--: -.:.1 .is done: -, _._;: - nples are measured as shown in Table 1.
    [0020] Table 1 Ownership of ZD-u Needle Reactivity Bale Etan Abbreviation Temperature I P25 NF EN 1426 TBA ° C NF EN 1 - F2 .. Bitumen Different bituminous B4, B5 6 and B7 are prepared at from the following products a base Ii .. grade 7 () 0, flow - having a penetrability 13, -, Ç of 69 1/10 mm and a TBA of 47.6 ° C and commercially available from the TOTAL group under: nargue AZA a 35/50 bit - e base, rated B1, having a penetration P25 of 41 1/10 mm and a TBA of 52.6 ° C and commercially available from the TOTAL group under the trademark AZALT; a styrene / butadiene diblock era, noted SE. a mass of styrene of 30% relative to the weight of the copolymer, commercially available from KRATON under the name D1184, a Fischer-Tropsch wax commercially available from SASOL under the trade name Sasob, a chemical additive, 3-bisdibutyl-4-hydroxyphenolpropionohydrazide, hydrazide; a poly (ethylene oxide) wax, denoted EO, commercially available from floneywel; an olefin-resistant polymer adjuvant in a terpolymer / butyl acrylate / methacrylate dr idyic, note E / AB / MG, in mass proportions, respectively 70 /:. having a Melt Flow Rate (MFR) (190 ° C / 2.16 kg) of 8 g / 10 min, calculated according to ASTM D1238-IS01133, the mass percentages used for each bitutene are shown in box 2 below. The quantity (4,1ditives for each bitumen is adjusted to obtain bitumens with equivalent mechanical properties, in particular a similar P25 penetration and TBA.) The bitumens are prepared in the following manner. Bo bitumen base in a reactor maintained at 165 ° C. with stirring at 300 rpm, then introduced into the Fischer-Tropsch i-42. The contents of the reactor are maintained at 165 ° C. with stirring at 300 rpm. for 1 hour Bitumen B.1 is prepared from bitumen bit Bo and POE wax in the same way as bitumen .02 2 3% Bitumen base B1 Sasobe Bitumen B2 Bo 97% G (1/10 mm ° C) TURB B4, intro t from ab 19 'min Then - Bo in - lL - the hyd respc', 0 ") C ante.
    [0021] For the bitumen 135 according to the invention, the bitumen base Bo is first introduced into a reactor at 160 ° C. with stirring at 400 rpm. Thereafter, the E / AB / M terpolymer is added and the mixture is stirred for about 2 hours. The mixture is granulated and the mixture is stirred for about 1 hour at 160 ° C. to obtain a homogeneous final pect. The mixture is cooled to room temperature. Bitumen B7 prepared from bitumen base has the same way as bitumen B5. For the bitumen introduced into a reactor maintained at 185 ° C. and with stirring at 300 rpm, the base bitut e copolymer SB. The reactor contents are then maintained at 185 ° C. with stirring. -, irs / min for 4 hours. Preparation of the GG granules: G8 Granules G7 to G7 are prepared from the Bo to B7 bitumens respectively according to the following method: first, a heating temperature denoted T 'is initially heated to 150 ° C. taken from the heat of a seringtk. In this case, it is difficult to form granules at this initial temperature, ie 1 ° C., at which point the temperature is raised to a higher temperature with an incrementation. 10 ° C until this shaping is possible.The bitumen drops are then allowed to cool to room temperature for 10 to 15 minutes, then the asphalt is covered with talc and sieved to remove Thus, bitumen granules are obtained (PC from bitumen 117 according to the control) (item 180) 0 B4 150 Lu heating temperature Te of the bitumen Ln of the gruiui1 / 4.J.LF% - The temperature of the bitumen B4, B5, B7 and B8 is lower than that of the bitumen bases Bo and I31 and the bitumen B6 comprising the copolymer SB The bitumens B4, B5, B7 and B8 are easily in the form of granules compared to the bitumens of the prior art. This test is carried out in order to evaluate the resistance to the load of granules Go to G8 at a temperature of 50 ° C. under a compressive force. Indeed, this test makes it possible to simulate the temperature and compression conditions of the granules on each other to which they are subjected during transport and / or storage in bulk in bags of 10 to 30 kg or in Big Bags of 500 to 1000 kg or in drums of 200 kg and to evaluate their resistance under these conditions. The load resistance test is carried out using a texture analyzer marketed 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 3 hours. 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 plunger, the compressive strength of the granules, including their appearance and ability to agglomerate, are visually evaluated. The observations are listed in Table 4 below. water 4 7, rennets Tarnished on charge o) in; Rats maintain their shape, but they must be. ++: the granules do not adhere to each other but no longer present their undulate form granules slightly adhere to each other. granules are as - -. The granules are G5 and G7, comprising the combination of hydrazide and E / AB / MG terpolymer and talc have a very good resistance where they are initial. The granules G4, G5, comp. Errature compared to the gr ns Go, G1, which will c aerate and / or for the port or nents ares. It is the case that the granules, and G6 will be less compared; the granules of bitumen are trar G3 and G6 agglo making difficult res and / or mipulation of said granule i7 and G8. vag bags, the dam; flee Big Ba_, urc- ace to stick
    权利要求:
    Claims (2)
    [0001]
    REVENDICATIONS1. Lime granules comprising at least one chemical additive selected from: a compound of general formula (I): R1- (COOH), wherein R1 is a linear or branched, saturated or unsaturated hydrocarbon chain comprising from 4 to 68 atoms carbon, preferably from 4 to 54 carbon atoms, more preferably from 4 to trombone atoms and z an integer ranging from 1 to 4, preferably from 2 to 4, and - a compound of the general formula (II: R- (NH ), CONH- (X) ', - NHCO (NH), - R' in which: R and R ', which may be identical or different, contain a linear or branched, cyclic or acyclic hydrocarbon-based saturated or unsaturated hydrocarbon chain, 1 to 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 a a plurality of hetero atoms and / or int cycles of 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.
    [0002]
    2. Bitumen granules according to claim 1, in which the chemical additive is a compound of general formula (I): R 1 - (COOH) 7. 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 an integer varying from 1 at 4, preferably from 2 to diaci (Bitumen granules according to Claim 1, in which the chemical additive is a compound of the general formula (II): R- (1 1H) 'NH- (X) -; in which: R and R ', which may be identical or different, contain a hydrocarbon, its ec or unsaturated, linear or branched, cyclic or acyclic having from 1 to 22 carbon atoms, optionally comprising H 2 O atoms having from 3 to and / or hetero, having atolue X contains a saturated or unsaturated, linear or branched, cyclic or acyclic, hydrocarbon chain having from 1 to 4 carbons having optionally one or more heteroatoms and / or atoms of heterocycles having of 3 atoms; nm are integers each independently of one another having a value of 0 or claim 5, wherein said compound comprises 0, and m is 0. 7. Granules What are the R, R, R, R, E, E, or DIFFERENCES. -_-... J. cyc. The polycyclic heterocycles may be aromatic to a number of hydroxyl groups and / or a hydrocarbon radical; or branched, having from 1 to 6 carbon atoms. ....... Bitumen granules according to claim 5, wherein said compound comprises two amide units when n has a value of 0 and has a value of 1. 9. Bitumen granules according to any one of claims 5 to 8, wherein said groups R aliphatic R ', which may be identical or different, comprise a hydrocarbon hydrocarbon hatrix, chosen in particular from groups C41-1, 1135, C181-1, H43, C22H45. 10. Bitumen granules according to any one of the preceding claims. wherein said X group comprises a carbon aliphatic hydrocarbon chain. Bitumen granules according to any one of claims 1 to 11, said granules comprising at least one olefinic polymer adjuvant functionalized with at least one of the glycidyl functional groups. Bitumen granules according to claim 12, wherein said olefinic polymer adjuvant is selected from the group consisting of (a) random or block copolymers of ethylene and a monomer selected from glycidyl acrylate and glycidyl methacrylate, comprising from 50% to 99.7% by weight of ethylene; (B) terpolymers, random or sequential, of ethylene, of a monomer A selected from vinyl acetate and C 1 -C 6 alkyl acrylates or methacrylates and a B monomer selected from acrylate of glycidyl and glycidyl methacrylate, comprising from 0.5% to 40% by weight of units derived from monomer A and from 0.5% to 15% by weight of units derived from monomer B, the remainder being formed from units from ethylene; and (c) copolymers resulting from the grafting of a monomer B selected from glycidyl acrylate and glycidyl methacrylate onto a substrate consisting of a polymer selected from polyethylenes, polypropylenes, random or block copolymers of ethylene and vinyl acetate and random or block copolymers of ethylene and C1-C6 alkyl acrylate or methacrylate, comprising from 40% to 99.7% by weight of ethylene, said graft copolymers comprising from 0.5% to 15% by weight of grafted units derived from monomer B. 245. Bitumen granules according to any one of claims 1 to 16, said granules being covered on at least a portion of their surface with an anti-blocking agent. agglomerating agent, preferably chosen from talc, fines, sand, cement, carbon, wood residues, plastic powder and glass powder, taken alone or as a mixture. 18. Bitumen granules according to claim 17, wherein the anti-caking agent is talc. 19. A method for transporting and / or storing road bitumen A -1, said road bitumen being transported and / or stored in the form of bitum granules as described in any one of claims 1 to 18. 20. Process according to claim 19, said bitumen being transported and / or stored at a temperature below 100 ° C, preferably at an ambient temperature below 100 ° C. 21. A process according to claims 19 and 20, wherein the road 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, more preferably between 50 ° C and 70 ° C, more preferably between 40 ° C and 60 ° C. 255
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    同族专利:
    公开号 | 公开日
    CN107075168A|2017-08-18|
    MA39895B1|2018-12-31|
    US20170226320A1|2017-08-10|
    EP3174925A1|2017-06-07|
    MA39895A1|2017-07-31|
    WO2016016318A1|2016-02-04|
    CA2956976A1|2016-02-04|
    FR3024456B1|2016-08-19|
    US10683422B2|2020-06-16|
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    法律状态:
    2015-07-27| PLFP| Fee payment|Year of fee payment: 2 |
    2016-02-05| PLSC| Search report ready|Effective date: 20160205 |
    2016-07-20| PLFP| Fee payment|Year of fee payment: 3 |
    2017-07-20| PLFP| Fee payment|Year of fee payment: 4 |
    2018-07-20| PLFP| Fee payment|Year of fee payment: 5 |
    2019-07-22| PLFP| Fee payment|Year of fee payment: 6 |
    2020-07-21| PLFP| Fee payment|Year of fee payment: 7 |
    2021-08-19| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1457538A|FR3024456B1|2014-08-01|2014-08-01|BITUMEN GRANULES|FR1457538A| FR3024456B1|2014-08-01|2014-08-01|BITUMEN GRANULES|
    MA39895A| MA39895B1|2014-08-01|2015-07-28|Road asphalt granules|
    EP15750656.9A| EP3174925A1|2014-08-01|2015-07-29|Road bitumen granules|
    PCT/EP2015/067407| WO2016016318A1|2014-08-01|2015-07-29|Road bitumen granules|
    CN201580046645.1A| CN107075168A|2014-08-01|2015-07-29|Road asphalt pelletizing|
    CA2956976A| CA2956976A1|2014-08-01|2015-07-29|Road bitumen granules|
    US15/501,121| US10683422B2|2014-08-01|2015-07-29|Road bitumen pellets|
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