SOLID BITUMEN AT AMBIENT TEMPERATURE

专利摘要:
Bitumen 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: an oil chosen from a hydrocarbon oil of petroleum or synthetic origin; at least one organogelling compound chosen from the compounds of general formula (I), (II) or (V). Process for the production of bitumen granules as well as their use as road binder, in particular for the manufacture of asphalt. Process for manufacturing asphalt from bitumen granules and a method for transporting and / or storing and / or handling bitumen granules
公开号:FR3059674A1
申请号:FR1662031
申请日:2016-12-07
公开日:2018-06-08
发明作者:Mouhamad MOUAZEN
申请人:Total Marketing Services SA；
IPC主号:

专利说明:

® FRENCH REPUBLIC
NATIONAL INSTITUTE OF INDUSTRIAL PROPERTY © Publication number:
(to be used only for reproduction orders)
©) National registration number
059 674
62031
COURBEVOIE © Int Cl ⁸ : C 08 L 95/00 (2017.01), C 09 D 191/00, C 10 C 3/14, E01 C 7/18, C 04 B 26/26
A1 PATENT APPLICATION
®) Date of filing: 07.12.16.(© Priority: © Applicant (s): TOTAL MARKETING SERVICES - FR. @ Inventor (s): MOUAZEN MOUHAMAD. ©) Date of public availability of the request: 08.06.18 Bulletin 18/23. ©) List of documents cited in the preliminary search report: See the end of this booklet (© References to other related national documents: ® Holder (s): TOTAL MARKETING SERVICES. ©) Extension request (s): (© Agent (s): PACT-IP.
FR 3 059 674 - A1
154; SOLID bitumen with AMBIENT TEMPERATURE.
©) Bitumen 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:
an oil chosen from a hydrocarbon oil of petroleum or synthetic origin, at least one organogelling compound chosen from the compounds of general formula (I), (II) or (V).
Process for the production of bitumen granules and their use as a road binder, in particular for the manufacture of asphalt.
Process for the manufacture of asphalt mixes from bitumen granules as well as a method for transporting and / or storing and / or handling bitumen granules.
FR Text deposit i
SOLID BITUMEN WITH AMBIENT TEMPERATURE Technical area
The present invention relates to a bitumen composition in divided form, solid at room temperature. The present invention also relates to a process for the preparation of a solid bitumen composition at ambient temperature as well as to its use as a road binder, in particular for the manufacture of mixes.
The present invention also relates to a process for the manufacture of mixes from solid bitumen according to the invention as well as a process for transport and / or storage and / or handling of a composition of solid bitumen at room temperature according to the invention. 'invention.
State of the prior 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 when heated.
In general, bitumen is stored and transported hot, in bulk, in tankers or by ships 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 to be dangerous and it is highly regulated from a regulatory point of view. This mode of transport does not present any particular difficulties when the transport equipment and infrastructure 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 journey that is too long. Bitumen delivery distances are therefore limited. On the other hand, keeping the bitumen at high temperatures in the tanks or in the tankers consumes energy. In addition, keeping the bitumen at high temperatures for a long time can affect the properties of the bitumen and thus change the final performance of the mix.
To overcome the problems of transport and storage of hot bitumen, packaging allowing the transport and storage of bitumen at room temperature has been developed. This mode of transporting 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 geographic regions of difficult and expensive access by traditional means of transport.
As an example of packaging allowing cold transport currently used, mention may be made of the packaging of bitumen at room temperature in
FR Text deposit of metal drums. This means is increasingly questionable from an environmental point of view because the bitumen stored in barrels must be reheated before its use as a road binder. However, this operation is difficult to implement for this type of packaging and the drums constitute 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 during transfer to the tanks of the asphalt production units. As for the handling and transportation of bituminous products in these drums, they can be difficult and dangerous if specialized equipment for handling drums is not available from carriers or at the place of use of bitumen.
Other examples of packaging include bitumens 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 describes bitumen granules covered with a powdery material, such as limestone powder. However, this type of bitumen in granules does not prevent the creep of the bitumen, especially at high ambient temperature.
Application WO2009 / 153324 describes bitumen granules coated with a polymeric anti-caking compound, in particular polyethylene. The disadvantage of this coating is that it modifies the properties of the bitumen during its road application.
Application WO 2016/016318 describes bitumen granules comprising a chemical additive which can be a mono or a polyacid, a hydrazide, or a diamide. These bitumen granules allow the transport and / or storage and / or handling of the bitumen at room temperature without it leaking, as well as the reduction of their adhesion and agglomeration therebetween.
Application US 2011/0233105 describes solid asphalt at room temperature in the form of granules comprising a core and a coating layer. The core is made from recycled materials and an asphalt binder. The coating layer may include one or more water resistant polymers, wax or fines. The purpose of this coating layer is to prevent particles from sticking to each other, but also to adjacent surfaces during storage. This document does not disclose the content of viscosifying compound relative to the total mass of the coating layer. It also does not disclose the viscosity of the compounds used in the composition of the coating layer.
The Applicants have therefore sought to develop bitumens capable of being subjected to high ambient temperatures without leaking, in particular bitumens
FR Text deposit in the form of granules whose adhesion and agglomeration during their transport and / or storage and / or handling at high ambient temperature is reduced compared to the granules of the prior art.
There is therefore a need to provide a transportable and / or storable bitumen composition and / or which can be handled at ambient temperature, making it possible to remedy the drawbacks of the prior art.
An objective of the present invention is to provide a transportable and / or storable and / or manipulable bitumen composition at elevated ambient temperature, the properties of which are preserved over time.
In particular, the object of the present invention is to provide a transportable and / or storable bitumen composition for a period greater than 2 months, preferably 3 months, and at elevated ambient temperature, in particular at a temperature below 100 ° C. , preferably from 20 ° C to 80 ° C.
Another objective of the invention is to provide an easily handled bitumen composition, in particular at high ambient temperature, in particular at a temperature up to 100 ° C., preferably from 20 ° C. to 80 ° C.
In particular, the aim of the present invention is to provide a bitumen composition which can be easily handled after a prolonged period of transport and / or storage at high ambient temperature, in particular during a period of transport and / or storage greater than 2 months, preferably greater than 3 months, and at a temperature of up to 100 ° C, preferably between 20 ° C and 80 ° C.
An object of the present invention is to provide a composition of bitumen in a form which allows its flow in solid form at room temperature, so that it can be handled without loss of material. We have sought to provide a bitumen composition which is in a form which makes it possible to condition it in a package, to decondition it, to transfer it to equipment, even at a high ambient temperature, without the need to heat it, and without loss. matter. The bitumen offered is in divided form and solid at room temperature so that it satisfactorily solves the problems mentioned above.
Another objective is to propose an industrial and economical process for manufacturing a transportable and / or storable bitumen composition and / or which can be handled at ambient temperature.
Another objective of the invention is to propose an industrial and economical process for manufacturing asphalt mixes from a transportable and / or storable bitumen composition and / or which can be handled at ambient temperature.
FR Text deposit
Another objective of the invention is to propose an ecological and economical process for transporting and / or storing and / or handling a composition of bitumen at room 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 making it possible to minimize the presence of waste and / or residues.
Summary of the invention
The invention relates to a bitumen solid at room 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:
• an oil chosen from a hydrocarbon oil of petroleum or synthetic origin, • at least one organogelling compound chosen from the compounds of general formula (I), (II) or (V):
Arl-Ri-Ar2 (I) in which:
Arl and Ar2 independently of one another represent a benzene ring or a system of condensed aromatic rings of 6 to 20 carbon atoms, substituted by at least one hydroxyl group, and optionally substituted by one or more C1- alkyl groups C20, and
Ri represents an optionally substituted divalent radical, the main chain of which comprises from 6 to 20 carbon atoms and at least one group chosen from the amide, ester, hydrazide, urea, carbamate, anhydride functions;
R ₂ - (NH) „CONH- (X) _m - (NHCO) p (NH)„ - R ₂ '(II) in which:
the groups R ₂ and R ₂ ', identical or different, represent a saturated or unsaturated, linear, branched or cyclic hydrocarbon chain, comprising from 1 to 22 carbon atoms, optionally substituted, and optionally comprising one or
FR Text depositing several heteroatoms such as N, O, S, C5-C24 hydrocarbon rings and / or C4-C24 hydrocarbon heterocycles comprising one or more heteroatoms such as N, O, S, and R2 ’can be H;
group X represents a hydrocarbon chain, saturated or unsaturated, linear, cyclic or branched, comprising from 1 to 22 carbon atoms, optionally substituted, and optionally comprising one or more heteroatoms such as N, O, S, C5 hydrocarbon rings -C24 and / or C4-C24 hydrocarbon heterocycles comprising one or more heteroatoms such as N, O, S;
n, m and p are integers having a value of 0 or 1 independently of each other;
R ₅ - (COOH) _z (V) in which:
R5 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 varying from 2 to 4.
According to a preferred embodiment, the hydrocarbon oil is chosen from hydrocarbon oils of petroleum origin.
According to a preferred variant, the hydrocarbon oil is chosen from aromatic oils having a content of aromatic compounds of between 30 and 95% by mass, advantageously between 50 and 95% by mass, more advantageously between 60 and 95% by mass relative to the total mass of the aromatic oil.
According to another preferred variant, the hydrocarbon oil is chosen from paraffinic oils having a total content of paraffinic compounds of at least 50% by mass relative to the total mass of the paraffinic oil.
Advantageously, according to this variant, the paraffinic oil has the respective contents:
(i) a total content of paraffinic compounds of between 50% and 90%;
FR Text deposit (ii) a total content of naphthenic compounds between 5% and 25%; and (iii) a total content of aromatic compounds of between 5% and 25%, the percentages being expressed by mass relative to the total mass of the paraffinic oil.
According to a preferred embodiment, the coating layer comprises from 80% to 99.9% of at least one oil, by mass relative to the total mass of the coating layer.
According to a preferred embodiment, the coating layer comprises from 0.1 to 10%, preferably from 0.2% to 5% by mass, more preferably from 0.5% to
3.5% by mass of organogelling compound relative to the total mass of the coating layer.
According to a preferred embodiment, the heart also comprises at least one compound chosen from the organogelling compounds s.
According to another preferred embodiment, the core further comprises at least one pitch having a penetrability at 25 ° C ranging from 0 to 20 1/10 mm, a ball and ring softening temperature (TBA) ranging from 115 ° C to 175 ° C, it being understood that the penetrability is measured according to standard EN 1426 and that the TBA is measured according to standard EN 1427.
The invention also relates to a process for manufacturing a bitumen as described above and in detail below, this process comprising:
i) forming the core from at least one bitumen base, ii) coating the core over all or part of its surface with a coating composition, iii) optionally, drying the granules obtained with 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.
FR Text deposit
The invention also relates to a bituminous mix which comprises a bitumen as described above and in detail below and which also comprises aggregates and optionally mineral and / or synthetic fillers.
According to a preferred embodiment, the bituminous mix is a road mix, bituminous concrete, or bituminous mastic.
The invention also relates to a process for the manufacture of mixes comprising at least one road binder and aggregates, the road binder being chosen from the bitumens described above and in detail below, 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 of the aggregates with the road binder in a tank such as a kneader or a kneading drum,
- obtaining mixes.
According to a preferred embodiment, the method does not include a step of heating the road binder before it is mixed with the aggregates.
The invention also relates to a method of transport and / or storage of bitumen, said bitumen being transported and / or stored in the form of solid bitumen at room temperature as described above and in detail below.
detailed description
The objectives which the applicant has set for itself have been achieved by developing bitumen compositions in a divided form, having a core / shell structure, in which the core is based on bitumen and the coating layer, base of an oily gelled composition, gives the overall structure improved properties compared to the bitumen granules known from the prior art.
“Ambient temperature” means the temperature resulting from the climatic conditions under which the road bitumen is transported and / or stored and / or handled. More specifically, the ambient temperature is equivalent to the temperature reached during transport and / or storage and / or handling of road bitumen, being
FR Text deposit understood that the ambient temperature implies that no heat input is provided 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 ranging up to 100 ° C., preferably from 20 ° C. to 80 ° C.
By "bitumen solid at room temperature" is meant a bitumen having a solid appearance at room temperature whatever the conditions of transport and / or storage and / or handling. More specifically, the term “solid bitumen at room temperature” means a bitumen which retains its solid appearance throughout transport and / or storage and / or handling at room temperature, that is to say a bitumen which does not flow at room temperature under its own weight and more, which does not flow when subjected to pressure forces from the conditions of transport and / or storage and / or handling.
By “coating layer covering all in part of the surface of the heart” is meant that the coating layer covers at least 90% of the surface of the heart, preferably at least 95% of the surface of the heart, more preferably at least 99% of the surface of the heart.
By "penetrability" is meant here the so-called "needle penetration" measurement which is carried out by means of a standard test NF EN 1426 at 25 ° C (P25). This penetration characteristic is expressed in tenths of a millimeter (dmm or 1/10 mm). The penetration of the needle, measured at 25 ° C, according to the standardized test NF EN
1426, represents the measurement of the penetration into a bitumen sample, after a time of 5 seconds, of a needle whose weight with its support is 100g. The NF EN 1426 standard replaces the NF T 66-004 approved standard of December 1986 with effect from December 20, 1999 (decision of the Director General of AFNOR on November 20, 1999).
By "softening point" means the measurement known as "ring ball softening point" which is carried out by means of a standard test NF EN
1427. The ring ball softening point corresponds to the temperature at which a standard diameter steel ball, after passing through the material to be tested (glued in a ring), reaches the bottom of a standardized vase filled with a liquid that we heat gradually, and in which we immersed the device.
The expression “consists essentially of” followed by one or more characteristics, signifies that may be included in the process or the material of the invention, in addition to the components or steps explicitly listed, components or steps which do not significantly modify the properties and characteristics of the invention.
FR Text deposit
The expression "between X and Y" includes the limits, unless explicitly stated otherwise. This expression therefore means that the target interval includes the values X, Y and all the values going from X to Y.
A first object of the invention relates to a bitumen solid at room temperature in the form of granules 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:
• an oil chosen from a hydrocarbon oil of petroleum or synthetic origin, and • at least one organogelling compound.
- Bitumen base
Advantageously, the core or core of the solid bitumen granules according to the invention is prepared from a bitumen base, said core being prepared by bringing into contact:
- one or more bitumen bases, and
- optionally at least one organogelling compound,
- possibly a pitch,
- optionally at least one anti-caking compound.
Within the meaning 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 all bituminous compositions consisting of one or more bitumen bases and optionally comprising one or more additives. When said compositions are intended for a road application, they are more frequently referred to as "road bitumen". The invention also finds applications in fields other than the road sector.
Among the bitumen bases which can be used according to the invention, mention may first of all be made of bitumens of natural origin, those contained in deposits of natural bitumen, natural asphalt or the tar sands and the bitumens obtained 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 can be chosen from bitumen bases or mixtures of bitumen bases originating from the refining of crude oil, in particular bitumen bases containing asphaltenes
FR Text deposit or pitch. The bitumen bases can be obtained by conventional methods of manufacturing bitumen bases in a refinery, in particular by direct distillation and / or vacuum distillation of petroleum. These bitumen bases can be optionally visbreaked and / or deasphalted and / or air-rectified. It is common to carry out vacuum distillation of atmospheric residues from the atmospheric distillation of crude oil. This manufacturing process therefore corresponds to the succession of atmospheric distillation and vacuum distillation, the feedstock feeding the vacuum distillation corresponding to 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 feed usually consisting of distillates and heavy products from vacuum distillation of atmospheric residues from petroleum distillation. This process makes it possible to obtain a blown, or semi-blown or oxidized or air-rectified or partially air-rectified base.
The different 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 recycling base. Bitumen bases can be hard grade or soft grade bitumen bases.
According to the invention, for the conventional methods for manufacturing bitumen bases, the operation is carried out at manufacturing temperatures 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 heating vary according to the quantity of bitumen used and are defined by standard NF EN 12594.
According to the invention, the blown bitumens can be manufactured in a blowing unit, by passing a flow 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 durations typically between 30 minutes and 2 hours, continuously
FR Text deposit or in batches. The blowing time and 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 standard EN 1426 from 5 to 330 1/10 mm, preferably from 20 to 220 1 / 10 mm.
As is well known, the so-called “needle penetration” measurement is carried out by means of a standard test NF EN 1426 at 25 ° C. (P25) · This penetration characteristic is expressed in tenths of a millimeter (dmm or 1 / 10 mm). The needle penetration, measured at 25 ° C, according to the standard test NF EN 1426, represents the measurement of the penetration into a bitumen sample, after a time of 5 seconds, of a needle whose weight with its support is 100 g. The NF EN 1426 standard replaces the NF T 66-004 approved standard of December 1986 with effect from December 20, 1999 (decision of the Director General of AFNOR on November 20, 1999).
According to one embodiment of the invention, the bitumen base may also comprise at least one known elastomer for bitumen such as the copolymers SB (block copolymer of styrene and butadiene), SB S (block copolymer of styrene butadiene-styrene), SIS (styrene-isoprene-styrene), SBS * (styrene-butadiene-styrene block copolymer in star), SBR (styrene-b-butadiene-rubber), EPDM (modified ethylene propylene diene). These elastomers can also be crosslinked according to any known method, for example with sulfur. Mention may also be made of the elastomers produced from styrene monomers and butadiene monomers allowing crosslinking without crosslinking agent as described in documents WO2007 / 058994, WO2008 / 137394 and by the applicant in patent application WO2011 / 013073.
Advantageously, according to this embodiment of the invention, the bituminous composition of which the core of the granules is composed comprises from 0.5% to 15% by mass, preferably from 1% to 15% by mass, more preferably from 2% at 12% by mass of elastomer relative to the total mass of the core bituminous composition.
According to one embodiment of the invention, the bituminous composition of which the core of the granules is composed comprises at least one olefinic polymeric adjuvant.
FR Text deposit
Advantageously, according to this embodiment, the bituminous composition of which the core of the granules is composed comprises from 0.05% to 15% by mass, preferably from 0.1% to 10% by mass, more preferably from 0.5% at 6% by mass of the olefinic polymeric adjuvant relative to the total mass of said core.
According to one embodiment of the invention, the bituminous composition of which the core of the granules is composed comprises at least one pitch.
Advantageously, according to this embodiment, the bituminous composition forming the core of the granules comprises from 2 to 30% by mass of pitch relative to the total mass of the composition, preferably from 3 to 20% by mass of pitch relative to the total mass of the bituminous composition forming the core of the granules.
According to one embodiment of the invention, the bituminous composition of which the core of the granules is composed comprises at least one anti-caking agent.
Advantageously, according to this embodiment, the composition forming the core of the bitumen granules comprises between 0.5% and 20% by mass, preferably between 2% and 20% by mass, more preferably between 4% and 15% by mass. at least one anti-caking agent relative to the total mass of the bituminous composition forming the heart of said granules.
According to one embodiment of the invention, the bituminous composition of which the core of the granules is composed comprises at least one organogelling compound.
Advantageously, according to this embodiment, the composition forming the core of the bitumen granules comprises from 0.1% to 10% by mass, preferably from 0.2% to 5% by mass, more preferably from 0.5% to 3.5% by mass of organogelling compound relative to the total mass of the bituminous composition forming the heart of said granules.
- Olefinic polymer admixture
The olefinic polymeric adjuvant is preferably chosen from the group consisting of (a) ethylene / glycidyl (meth) acrylate copolymers; (b) the ethylene / monomer A / monomer B terpolymers and (c) the 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, preferably statistical, copolymers of ethylene and of a monomer chosen from glycidyl acrylate and methacrylate
FR Text glycidyl deposition, comprising from 50% to 99.7% by mass, preferably from 60% to 95% by mass, more preferably 60% to 90% by mass of ethylene.
(b) The terpolymers are advantageously chosen from random or block, preferably random, terpolymers of ethylene, of a monomer A and of a monomer B.
The monomer A is chosen from vinyl acetate and C1 to C6 alkyl acrylates or methacrylates.
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 mass, preferably from 5% to 35% by mass, more preferably from 10% to 30% by mass of units derived from monomer A and, 0.5% to 15% by mass, preferably 2.5% to 15% by mass of units derived from monomer B, the remainder being formed of units derived from ethylene.
(c) The copolymers result from the grafting of a monomer B chosen from glycidyl acrylate and glycidyl methacrylate, on a polymer substrate. The polymer substrate consists of a polymer chosen from polyethylenes, in particular low density polyethylenes, polypropylenes, random or block, preferably random copolymers, of ethylene and vinyl acetate and random or block copolymers, preferably random , ethylene and C1 to C6 alkyl acrylate or methacrylate, comprising from 40% to 99.7% by mass, preferably from 50% to 99% by mass of ethylene. Said graft copolymers comprise from 0.5% to 15% by mass, preferably from 2.5% to 15% by mass of grafted units originating from monomer B.
Advantageously, the olefinic polymer adjuvant is chosen from random terpolymers of ethylene (b), of a monomer A chosen from acrylates or methacrylates of C1 to G alkyl, and of a monomer B chosen from acrylate of glycidyl and glycidyl methacrylate, comprising from 0.5% to 40% by mass, preferably from 5% to 35% by mass, more preferably from 10% to 30% by mass of units derived from monomer A and, from 0 , 5% to 15% by mass, preferably from 2.5% to 15% by mass of units originating from monomer B, the remainder being formed of units originating from ethylene.
FR Text deposit
- Pitch:
The bitumen base is chemically different from the pitch used. Therefore, the bitumen base and the pitch cannot be used as a replacement for the other because their chemical characteristics are different. Pitch can be used as a mixture in the bitumen base.
According to one embodiment of the invention, the pitch is a blown pitch. Within the meaning of the invention, the terms "blown pitch" and "oxidized pitch" will be used independently of one another.
According to the French dictionary, "pitch" is understood to mean a residue from the distillation of petroleum tar, coal tar, wood or other organic molecules.
The pitch used in the invention is chosen from petroleum distillation residues, also called "petroleum pitch".
In the description, the terms "pitch", "oil pitch" and "deasphalting pitch" will be used independently of one another.
The pitches can be obtained by conventional refinery manufacturing processes. The manufacturing process corresponds to the succession of atmospheric distillation and vacuum distillation. First, the crude oil is subjected to distillation at atmospheric pressure, which leads to the production of a gas phase, various distillates and an atmospheric distillate residue. Then, the residue from atmospheric distillation is itself subjected to distillation under reduced pressure, called vacuum distillation, which makes it possible to separate a heavy diesel, various cuts of distillais and a residue of vacuum distillation. This vacuum distillation residue contains "pitch oil" in varying concentrations.
You can get the "petroleum pitch" by two methods: the ^era process:
The vacuum distillation residue is subjected to a desalphating operation by the addition of an appropriate solvent, such as propane, which thus makes it possible to precipitate the pitch and to separate it from light fractions such as deapphalted oil.
2 ^nd method:
The vacuum distillation residue is subjected to solvent extraction, and more specifically to furfural. This heterocyclic aldehyde has the particularity of selectively solubilizing aromatic and polycyclic compounds. This process thus makes it possible to eliminate the aromatic extracts and to recover the "oil pitch".
FR Text deposit
According to one embodiment, the pitch is an oxidized pitch.
Preferably, the oxidized pitch used according to the invention is obtained by oxidation of a mixture comprising pitch and a diluent, such as a light gasoline, also called “fluxing agent” subjected to an oxidation operation in a blowing tower. in the presence of a catalyst, at a fixed temperature and at a given pressure.
For example, oxidized pitches can be manufactured in a blowing unit, by passing a flow of air and / or oxygen through a starting pitch. This operation can be carried out in the presence of an oxidation catalyst, for example phosphoric acid. Generally, the oxidation is carried out at high temperatures, of the order of 200 to 300 ° C, for relatively long periods typically between 30 minutes and 2 hours, continuously or in batches. The duration and the temperature of oxidation are adjusted according to the properties targeted for the oxidized pitch and according to the quality of the starting pitch.
The mechanical qualities of pitches are generally assessed by determining a series of mechanical characteristics by standardized tests, the most widely used of which are the needle penetration expressed in 1/10 mm and the softening point determined by the ball and ring test. , also called ball and ring softening temperature (TBA).
According to one embodiment of the invention, the pitch exhibits needle penetration at 25 ° C from 0 to 20 1/10 mm, preferably from 0 to 15 1/10 mm, more preferably from 0 to 10 1 / 10 mm, it being understood that the penetrability is measured according to standard EN 1426.
According to one embodiment of the invention, the pitch has a softening point between 115 ° C and 175 ° C. Among examples of pitches used in the invention, there are pitches having respectively a softening point between 115 ° C and 125 ° C, between 135 and 145 ° C or even between 165 and 175 ° C.
The addition of a pitch with the mechanical characteristics presented above in a bituminous composition making up the core of the granules of the invention makes it possible to improve the modulus properties of said bituminous composition and also to improve the modulus properties of bituminous coated. In addition, the addition of pitch according to the invention in a bituminous composition making up the core of the granules of the invention makes it possible to reduce the penetrability and to increase the ball-ring softening temperature of said bituminous composition while maintaining the
FR Text deposit viscosity of said bituminous composition compared to a bituminous composition without pitch.
The bituminous composition making up the core of the granules of the invention can be prepared by a process comprising at least the steps of:
• Heating of the bitumen base to a temperature ranging from 140 to 180 ° C, • Introduction of pitch in the bitumen base, • Stirring of the mixture at a temperature ranging from 140 to 180 ° C until a mixture is obtained homogeneous.
It has been found that the pitch mixes perfectly with the bitumen base.
According to one embodiment of the invention, the pitch is in the form of granules before its introduction into the heated bitumen base. Such an embodiment facilitates the handling of the components and the implementation of the method.
Advantageously, the pitch does not need to be heated before being added to the bitumen base. Although the pitch usually has a melting temperature above 220 ° C., it dissolves in bitumens at the usual temperatures for preparing the bituminous compositions. The process for manufacturing the bituminous composition making up the core of the granules of the invention is easy to implement and does not require hot transporting over long distances the pitch intended to improve the properties of the bitumen base.
According to one embodiment of the invention, the pitch used in the process for producing the core of the granules is in cold solid form and divided, preferably in the form of granules. This form facilitates the handling of pitch for its implementation in the manufacture of the bituminous composition making up the core of the granules of the invention.
The term "solid pitch when cold and in divided form" means a pitch which is solid at room temperature and which is conditioned in a divided form, that is to say in the form of units which are distinct from each other, for example granules.
Pitch granules can have, within the same population of granules, one or more shapes chosen from a cylindrical, spherical or ovoid shape. More specifically, the pitch granules preferably have a cylindrical or spherical shape.
Advantageously, the size of the pitch granules is such that the longest average dimension is preferably less than or equal to 50 mm, more
FR Text deposit preferably from 2 to 30 mm. For example, the use of a die makes it possible to control the manufacture of granules of a chosen size. A sieving makes it possible to select granules according to their size.
To allow the formation of pitch granules which do not adhere to each other and resist compression during storage, it may be advantageous to use pitch granules coated in all or part of their surface with an anti-caking compound. Pitch, in the form of granules possibly covered by an anti-caking compound, is easily handled after a prolonged period of transport and / or storage. The anti-caking compound is then found in the composition forming the heart of the granules.
- Anti-caking agent:
The anti-caking compound can be used as an additive in the composition of which the heart of the granules is made.
It can also, optionally, be used to form a second coating layer, on all or part of the surface of the granules.
The anti-caking compound is of mineral or organic origin.
More preferably, the anti-caking compound is chosen from: talc; fines, also called fillers, generally with a diameter of less than 125 μm, such as siliceous fines, with the exception of limestone fines; ultrafines; sand such as Fontainebleau sand; cement ; carbon; wood residues such as lignin, lignosulfonate, powders of coniferous needles, powders of coniferous cones, in particular pine; rice husk ash; glass powder; clays such as kaolin, bentonite, vermiculite; alumina such as alumina hydrates; silica; silica derivatives such as silicates, silicon hydroxides and other silicon oxides; silica fumes; plastic powder; lime; the plaster ; rubber blowing snow; polymer powder, such as styrene-butadiene copolymers (SB), styrene-butadiene-styrene copolymers (SB S) and mixtures of these materials.
Advantageously, the anti-caking compound is chosen from: fines, generally of diameter less than 125 μm; silica fumes; wood residues such as lignin, conifer needle powders and conifer cone powders; their mixtures.
FR Text deposit
As an example, the anti-caking agent can be chosen from silica fumes. The silica fumes used in the invention are commercially available and for example can be sold by Evonik Degussa under the brand AEROSIL®, such as for example AEROSIL®200, by Cabot Corporation under the brands CAB-O-SIL® and CAB -O-SPERSE® or by Wacker Chemie AG under the brand HDK®.
- The composition forming the heart of the granules:
The composition forming the heart of the granules comprises:
- one or more bitumen bases, and
- optionally at least one organogelling compound,
- possibly a pitch.
Optionally, it can also include:
one or more additives chosen from elastomers, olefinic polymer adjuvants, anti-caking compounds.
Advantageously, the composition forming the core of the granules, comprising a bitumen base added with at least one organogelling compound and / or at least one pitch, has a targeted penetrability ranging from 5 to 45 l / 10mm and / or a ball softening temperature and ring (TBA) aimed greater than or equal to 90 ° C, it being understood that the penetrability is measured at 25 ° C according to standard EN 1426 and the TBA according to standard EN 1427.
These characteristics are achieved by methods known to a person skilled in the art, by hot mixing the different component (s) in the bitumen base in the appropriate quantities as indicated above for each category of component. The temperature of the bitumen base during the introduction of the additives is chosen according to their nature, in order to avoid their degradation. The agitation is more or less vigorous and more or less prolonged, in order to obtain a homogeneous composition without degrading the properties of the composition forming the heart of the granules.
The composition thus obtained is used directly in the process for manufacturing bitumen granules with a core / shell structure described below.
Advantageously, the bituminous composition forming the core of the granules comprises:
- one or more bitumen bases,
FR Text deposit
between 0.1% and 5% by mass, preferably between 0.5% and 4% by mass, more preferably between 0.5% and 2.5% by mass of at least one organogelling compound, relative to the total bitumen mass of said granules. Advantageously, the bituminous composition forming the core of the granules comprises:
- one or more bitumen bases,
between 0.1% and 5% by mass, preferably between 0.5% and 4% by mass, more preferably between 0.5% and 2.5% by mass of at least one organogelling compound relative to the total mass of bitumen of said granules, and
- between 0.5% and 20% by mass, preferably between 2% and 20% by mass, more preferably between 4% and 15% by mass of at least one anti-caking compound relative to the total mass of bitumen of said granules .
- Oil:
Preferably, the oil is a hydrocarbon oil of petroleum origin. It can be of aromatic or paraffinic type.
According to one embodiment, the oil is composed of 90 to 100% by mass of at least one hydrocarbon oil of petroleum origin, advantageously of 95 to 100%, even better of 98 to 100% by mass of at least a hydrocarbon oil of petroleum origin. Even more advantageously, the oil consists of a hydrocarbon oil of petroleum origin or of a mixture of hydrocarbon oils of petroleum origin.
In a preferred embodiment of the invention, the hydrocarbon oil of petroleum origin is chosen from aromatic oils.
More preferably, the aromatic oils have a content of aromatic compounds of between 30 and 95% by mass, advantageously between 50 and 95% by mass, more advantageously between 60 and 95% by mass relative to the total mass of the aromatic oil (SARA method: Saturated / Aromatic / Resins / Asphaltenes).
More preferably, the aromatic oils have a content of saturated compounds of between 1 and 20% by mass, advantageously of between 3 and 15%.
FR Mass deposit text, more advantageously between 5 and 10% by mass (SARA method: Saturated / Aromatic / Resins / Asphaltenes).
More preferably, the aromatic oils have a content of resin compounds of between 1 and 10% by mass, advantageously between 3 and 5% by mass, (SARA method: Saturated / Aromatic / Resins / Asphaltenes).
The contents of saturated, resin and aromatic compounds mentioned in the present application are determined according to standard ASTM D2140, in% by mass relative to the mass of the oil.
More preferably, the aromatic oils have a kinematic viscosity at 100 ° C of between 0.1 and 150 mm ² / s, advantageously between 5 and 120 mm ² / s, more advantageously between 7 and 90 mm ² / s (Method ASTM D 445).
More preferably, aromatic oils have a Cleveland flash point
O O O greater than or equal to 150 C, advantageously between 150 C and 600 C, more advantageously between 200 C and 400 C (Method EN ISO 2592).
More preferably, the aromatic oils have an aniline point of between 20 ° C. and 120 ° C., advantageously between 40 ° C. and 120 ° C. (Method ASTM D611).
O
More preferably, the aromatic oils have a density at 15 C of between 400 kg / m ³ and 1500 kg / m ³ , advantageously between 600 kg / m ³ and 1200 kg / m ³ , more advantageously between 800 kg / m ³ and 1000 kg / m ³ (ASTM D4052 method).
According to this advantageous embodiment, the aromatic oil comprises aromatic extracts of petroleum residues, obtained by extraction or dearomatization of residues from distillation of petroleum fractions.
Aromatic extracts are secondary products of the refining process of crude oils, obtained in particular from the products of vacuum distillation of atmospheric residues. They result from a simple or a double extraction of the raffinai recoverable in lubricants, using a polar solvent.
The different extracts are classified into different categories according to their process of obtaining and are as follows:
FR Text deposit
- DAE (Distillate Aromatic Extract in English, or aromatic extract of distillate)
- MES (Mild Extract Solvate in English or mild extraction solvent),
- TDAE (Treated Distillate Aromatic Extract in English or treated aromatic distilled extract),
- RAE (Residual Aromatic Extract in English or residual aromatic extract),
- TRAE (Treated Residual Aromatic Extract in English or residual aromatic extract treated)
For example, the aromatic oils which can be used according to the invention can be chosen from the following products sold by the company TOTAL under the names: Plaxolene 50® (also sold under the trade name Régénis 50®), Plaxolene TD346® and Plaxolène MS 132® .
The respective contents of paraffinic, naphthenic and aromatic compounds depend to some extent on the nature of the crude oil which produces the aromatic oil and the refining process used.
According to one embodiment, the oil is composed of 90 to 100% by mass of at least one oil of aromatic petroleum origin and 0 to 10% by mass of one or more other oils.
For example, the Régénis 50 ® is an RAE (Residual Aromatic Extract) which has:
a density at 15 ° C of between 980 kg / m ³ and 1010 kg / m ³ (ASTM D4052 method),
- a flash point (Cleveland) of around 230 ° C (EN ISO 2592 method),
- a kinematic viscosity at 100 ° C between 60 and 85 mm ² / s (ASTM D 445 method), an aniline point between 53 and 65 ° C (ASTM D611 method).
For example, Plaxolene TD346 ® is a TDAE (Treated Distillâtes Aromatic Extract) which has:
- a density at 15 ° C of between 940 kg / m ³ and 970 kg / m ³ (Method
ASTM D4052),
- a flash point (Cleveland) of around 220 ° C (EN ISO 2592 method),
FR Text deposit
- a kinematic viscosity at 100 ° C between 16 and 23 mm ² / s (ASTMD445 method), an aniline point between 64 and 72 ° C (ASTM D611 method).
For example, Plaxolene MS 132 ® is a MES (Mild Extract Solvate) which has:
a density at 15 ° C of between 895 kg / m ³ and 925 kg / m ³ (ASTM D4052 method),
- a flash point (Cleveland) of around 230 ° C (EN ISO 2592 method),
- a kinematic viscosity at 100 ° C between 13 and 17 mm ² / s (ASTM D 445 method), an aniline point between 85 and 100 ° C (ASTM D611 method).
According to a second advantageous embodiment, the oil is a paraffinic oil mainly comprising paraffinic extracts of petroleum residues. According to this specific embodiment, advantageously, the oil comprises a total content of paraffinic compounds of at least 50% by mass, preferably at least 60% by mass, for example between 50% and 90%, of preferably between 60% and 90%, more preferably between 50% and 80% and in particular between 55% and 70%, or in particular between 60% and 75%.
In a more specific embodiment, the oil also contains a total content of naphthenic compounds which does not exceed 25%, for example between 5% and 25%, and in particular between 10% and 25%.
In a more specific embodiment, the oil also contains a total aromatic content which does not exceed 25%, for example between 5% and 25%, and in particular between 8% and 18%.
In a particularly preferred embodiment, the oil is a paraffinic oil, comprising the respective contents:
(i) a total content of paraffinic compounds of between 50% and
90%;
(ii) a total content of naphthenic compounds of between 5% and 25%; and (iii) a total content of aromatic compounds of between 5% and 25%.
In a more particularly preferred embodiment, the oil is a paraffinic oil, comprising the respective contents:
FR Text deposit (i) a total content of paraffinic compounds between 60% and 75%;
(ii) a total content of naphthenic compounds of between 5% and 25%; and (iii) a total content of aromatic compounds of between 5% and 25%.
In a still preferred embodiment, the oil is a paraffinic oil
DAO, including the respective contents:
(i) a total content of paraffinic compounds of between 60% and 75%;
(ii) a total content of naphthenic compounds of between 15% and 25%; and (iii) a total content of aromatic compounds of between 10% and 15%.
In a preferred embodiment of the invention, the paraffinic oils are obtained from deasphalting cuts of distillation under reduced pressure (residue under vacuum, RSV) of crude oil (hereinafter referred to as "CAD oil"). The principle of deasphalting is based on a precipitation separation of an oil residue into two phases: i) a phase known as deasphalted oil, also called oil matrix or oil phase or DAO (DeAsphalted Oil in English); and ii) a so-called asphalt phase.
Oils corresponding to the characteristics below and which can be used according to the invention are obtained by the processes for deasphalting of vacuum residues (RSV) from petroleum refining, for example by deasphalting with a C3 solvent. C6, preferably propane. Deasphalting methods are well known to those skilled in the art and are described for example in FR3014111, US 2004/0069685, US 4,305,812 and US 4,455,216 or in Lee et al., 2014, Fuel Processing Technology 119: 204-210.
In Lee et al., 2014, Fuel Processing Technology 119: 204-210, the residues resulting from vacuum distillation (RSV) are separated according to their molecular mass in the presence of solvent C3 to C6 (for example propane). The so-called DAO oil thus obtained is rich in paraffin, has a very low asphaltene content, has an evaporation temperature between 440 ° C and 750 ° C, and an API gravity much higher than that of vacuum residues.
The respective levels of paraffinic, naphthenic and aromatic compounds depend to some extent on the nature of the crude oil that produces the CAD oil and the refining process used. A person skilled in the art knows how to determine the respective contents of paraffinic, naphthenic and aromatic compounds of a
FR Text deposit DAO oil for example using the SARA fractionation method also described in Lee et al 2014, Fuel Processing Technology 119: 204-210 and thus select the appropriate DAO oil for the preparation of the oil composition gelled according to the invention.
The contents of paraffinic, naphthenic and aromatic compounds mentioned in the present application are determined according to standard ASTM D2140, in% by mass relative to the mass of the oil.
According to an advantageous embodiment, the oil is composed of a mixture based on an aromatic hydrocarbon oil and a paraffinic oil.
According to an advantageous embodiment, the oil is composed of 90 to 100% by mass of at least one aromatic oil, preferably an RAE oil, and from 0 to 10% by mass of one or more other oils.
According to an advantageous embodiment, the oil is composed of 90 to 100% by mass of at least one paraffinic oil, preferably a DAO oil, and from 0 to 10% by mass of one or more other oils.
Preferably, the oil is a paraffinic oil, advantageously a DAO paraffinic oil.
The other oils used can be chosen from petroleum oils, vegetable oils and mixtures thereof.
For example, oils of vegetable origin can be chosen from rapeseed, sunflower, soybean, flax, olive, palm, castor, wood, corn, squash, grapeseed oils. , jojoba, sesame, walnut, hazelnut, almond, shea, macadamia, cotton, alfalfa, rye, safflower, peanut, coconut and copra, and mixtures thereof.
The organogelling compound
The coating layer of bitumen solid at room temperature in the form of granules according to the invention comprises at least one organogelling compound.
The core of the bitumen solid at room temperature in the form of granules according to the invention can also comprise at least one organogelling compound.
FR Text deposit
In particular, the coating layer comprises at least one organogelling compound in an amount suitable for this composition to form a solid coating at room temperature.
Preferably, the composition forming the core of the bitumen granules solid at room temperature comprises at least one organogelling compound in an amount suitable for this composition to be solid at room temperature and in divided form.
In one embodiment of the invention, the organogelator is an organic compound. Advantageously, the organogelling compound has a molar mass less than or equal to 2000 gmol ' ¹ , preferably a molar mass less than or equal to 1000 gmol' ¹ .
In this embodiment, according to a first variant, the organogelling compound is a compound of general formula (I):
Arl-Ri-Ar2 (I), in which:
• Arl and Ar2 represent, independently of each other, a benzene ring or a system of condensed aromatic rings of 6 to 20 carbon atoms, substituted by at least one hydroxyl group and optionally substituted by one or more C1- alkyl groups C20, and • Ri represents an optionally substituted divalent radical, the main chain of which comprises from 6 to 20 carbon atoms and at least one group chosen from the amide, ester, hydrazide, urea, carbamate and anhydride functions.
Preferably, Arl and / or Ar2 are substituted by at least one alkyl group of 1 to 10 carbon atoms, advantageously in one or more positions ortho with respect to the hydroxyl group (s), more preferably Arl and Ar2 are 3,5dialkyl-4-hydroxyphenyl groups, preferably 3,5-di- / c / 7-butyl-4hydroxyphenyl groups.
Preferably, Ri is in the para position with respect to a hydroxyl group of Arl and / or Ar2.
As an example of a compound of formula (I), mention may be made of 2 ′, 3-bis [(3- [3, 5-dife / 7-butyl-4-hydroxyphenyl] propionyl)] propionohydrazide.
FR Text deposit
According to a second variant of this embodiment, the organogelling compound is a compound of general formula (II):
R ₂ - (NH) „CONH- (X) _m -NHCO (NH)„ - R ₂ '(II), in which,
the groups R ₂ and R ₂ ′, which are identical or different, represent a saturated or unsaturated, linear, branched or cyclic hydrocarbon chain, comprising from 1 to 22 carbon atoms, optionally substituted by one or more hydroxyl groups or amine groups, and optionally comprising heteroatoms such as N, O, S, Cs-C ₂ 4 hydrocarbon rings and / or C4-C ₂ 4 hydrocarbon heterocycles comprising one or more heteroatoms such as N, O, S;
- the group X represents a hydrocarbon chain, saturated or unsaturated, linear, cyclic or branched, comprising from 1 to 22 carbon atoms, optionally substituted, and optionally comprising heteroatoms such as N, O, S, Cs hydrocarbon rings- _C2 4 and / or hydrocarbon heterocycles _C4-C2 4 including one or more heteroatoms such as N, O, S;
- n and m are integers having a value of 0 or 1 independently of each other.
According to this variant, when the integer has a value of 0, then the groups R ₂ - (NH) _n CONH and NHCO (NH) _n -R ₂ 'are covalently linked and together form a hydrazide CONH-NHCO bond. The group R ₂ , or the group R ₂ ', then represents at least one group chosen from: a hydrocarbon chain of at least 4 carbon atoms, an aliphatic ring of 3 to 8 atoms, an aliphatic condensed polycyclic system, partially aromatic or entirely aromatic, each cycle comprising 5 or 6 atoms.
Still according to this variant, when the integer has a value of 1, then the group R ₂ , the group R ₂ 'and / or the group X, represents at least one group chosen from: a hydrocarbon chain of at least 4 atoms carbon, an aliphatic ring of 3 to 8 atoms, an aliphatic condensed polycyclic system, partially aromatic or fully aromatic, each cycle comprising 5 or 6 atoms.
Preferably, the group R ₂ and / or R ₂ 'represents an aliphatic hydrocarbon chain of 4 to 22 carbon atoms, in particular, chosen from the groups
C4H9, C5H11, C9H19, CnH ₂₃ , Ci ₂ H ₂₅ , C17H35, C18H37, C ₂ 1H43, C ₂₂ H45.
FR Text deposit
According to a first preferred embodiment, the group X represents a linear, saturated hydrocarbon chain comprising from 1 to 22 carbon atoms, advantageously from 1 to 12 carbon atoms, even better still from 1 to 10 carbon atoms. Preferably, the group X is chosen from the groups C2H4, C ₃ H ₆ .
According to a second preferred embodiment, the group X can also be a cyclohexyl group or a phenyl group, the radicals R2- (NH) _n CONH- and NHCO (NH) _n -R ₂ 'can then be in the ortho, meta position or para. Furthermore, the radicals R ₂ - (NH) _n CONH- and -NHCO (NH) _n -R ₂ 'can be in the cis or trans position relative to each other. In addition, when the radical X is cyclic, this ring can be substituted by other groups than the two main groups R ₂ (NH) „CONH- and -NHCO (NH)„ - R ₂ '.
According to a third preferred embodiment, the group X represents two cycles of 6 carbons, optionally substituted, linked by a CH ₂ group, these cycles being aliphatic or aromatic. In this case, the group X is for example:
Advantageously, according to this variant, the organogelling compound is a compound of general formula (II) chosen from hydrazide derivatives such as the compounds C5H11-CONH-NHCO-C5H11, C9H19-CONH-NHCO-C9H19, CnH ₂₃ -CONHNHCO-ChH ₂₃ , Ci ₇ H ₃₅ -CONH-NHCO-Ci ₇ H ₃₅ , or C ₂ iH ₄₃ -CONH-NHCO-C ₂ iH ₄₃ ; diamides such as N, N'-ethylenedi (laurylamide) of formula CnH ₂₃ -CONH-CH ₂ CH ₂ -NHCO-ChH ₃ i, N, N'-ethylenedi (myristylamide) of formula Ci ₃ H ₂₇ -CONHCH ₂ -CH ₂ -NHCO-Ci ₃ H ₂₇ , the N, N'-ethylenedi (palmitamide) of formula C15FF1-CONHCH ₂ -CH ₂ -NHCO-Ci5H ₃ i, the N, N'-ethylenedi (stearamide) of formula Ci ₇ H ₃₅ -CONHCH ₂ -CH ₂ -NHCO-Ci ₇ H ₃₅ ; and ureide derivatives such as 4,4'bis (dodecylaminocarbonylamino) diphenylmethane of formula Ci ₂ H ₂₅ -NHCONHC ₆ H ₄ -CH ₂ -C ₆ H ₄ -NHCONH-C i ₂ H ₂₅
According to a third variant, the organogelling compound is a compound of formula (III):
ICG70130EN Text deposit (R-NHCO) _X -Z- (NHCO-R ') y (III), in which,
- R and R ', identical or different, represent a saturated or unsaturated, linear, branched or cyclic hydrocarbon chain comprising from 1 to 22 carbon atoms, optionally substituted, and optionally comprising heteroatoms such as N, O, S, rings C5-C24 hydrocarbons and / or C4-C24 hydrocarbon heterocycles comprising one or more heteroatoms such as N, O, S,
- Z represents a tri-functionalized group chosen from the following groups:
- x and y are different integers with a value varying from 0 to 3 and such that x + y = 3.
Preferably, when x is equal to 0 and Z represents Z ₂ , the compound of formula (III) is N2, N4, N6-tridecylmelamine having the following formula with R 'representing the group C9H49:
HN
WE
Λ.Λ.Λ
C ₉ H _1f r N rl
NH
Λ
CaH
9 ⁿ 19
Other preferred compounds corresponding to formula (III) are such that x is equal to 0, Z represents Z ₂ and R ′ represents a saturated, linear hydrocarbon chain, from 1 to 22 carbon atoms, preferably from 2 to 18 carbon atoms, preferably 5 to 12 carbon atoms.
Other preferred compounds corresponding to formula (III) are such that: y is equal to 0 and Z represents Zi, the compounds then have the formula:
ICG70130FR Text deposit
with R chosen from the following groups, taken alone or as a mixture:
Other preferred compounds corresponding to formula (III) are such that: y is equal to 5 to 0, Z represents Zi and R represents a saturated, linear hydrocarbon chain of 1 to carbon atoms, preferably of 8 to 12 atoms of carbon.
According to a fourth variant, the organogelling compound is a reaction product of at least one C3-C12 polyol and at least one C ₂ -Ci ₂ aldehyde. Among the polyols which can be used, mention may be made of sorbitol, xylitol, mannitol and / or ribitol. Preferably, the polyol is sorbitol.
Advantageously, according to this variant, the organogelling compound is a compound which comprises at least one function of general formula (IV):
^R (IV) with:
- x is an integer,
- R is chosen from a C1-C12 alkyl, C2-C12 alkenyl, G, C12 aryl, or C7-C12 aralkyl radical, optionally substituted by one or more halogen atoms, one or more C1 alkoxy groups -G
FR Text deposit
According to this variant, the organogelling compound is advantageously 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. By this condensation reaction, sorbitol acetals, which are derivatives of sorbitol, are obtained. The 1,3: 2,4-Di-O-benzylidene-D-sorbitol is obtained by reacting 1 mole of D-sorbitol and 2 moles of benzaldehyde and has the formula:
The sorbitol derivatives may thus be all the condensation products of aldehydes, in particular of aromatic aldehydes with sorbitol. We will then obtain sorbitol derivatives of general formula:
where Ari and Ar ₂ are optionally substituted aromatic rings.
Among the sorbitol derivatives, 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-monoO-benzylidene-D-sorbitol, l, 3: 2,4-bis (p-methylbenzylidene) sorbitol, 1,3: 2,4bis (3,4-dimethylbenzylidene) sorbitol, l, 3: 2,4-bis (p-ethylbenzylidene) sorbitol, l, 3: 2,4-bis (p-propylbenzylidene) sorbitol, l, 3: 2,4-bis (p-butylbenzylidene) sorbitol, l, 3: 2,4-bis (p-ethoxylbenzylidene) sorbitol, 1,3: 2,4-bis (p-chlorobenzylidene) sorbitol, 1,3: 2,4-bis (p-bromobenzylidene) sorbitol, 1,3: 2,4-Di-O-methylbenzylidene-Dsorbitol, l, 3: 2,4-Di-O-dimethylbenzylidene-D-sorbitol, l, 3: 2,4-Di-O- (4methylbenzylidene) -D-sorbitol, 1,3: 2,4-Di-O- (4,3-dimethylbenzylidene) -D-sorbitol.
FR Text deposit
Preferably, according to this variant, the organogelling compound is 1,3: 2,4-Di-Obenzylidene-D-sorbitol.
According to a fifth variant, the organogelling compound is a compound of general formula (V):
R ₅ - (COOH) _z (V), in which R5 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 atoms of carbon and z is an integer varying from 2 to 4.
Preferably, the group R5 is a saturated linear chain of formula C _w H _2w with w an integer varying from 4 to 22, preferably from 4 to 12.
According to this variant of the invention, the organogelling compounds corresponding to formula (V) can be diacids (z = 2), triacids (z = 3) or tetracids (z = 4). The preferred organogelling compounds according to this variant are diacids with z = 2.
Preferably, according to this variant, the diacids (V) have the general formula HOOC-C _w H _2w -COOH with w an integer varying from 4 to 22, preferably from 4 to 12.
Advantageously, according to this variant, the organogelling compound is a diacid chosen from adipic acid or 1,6-hexanedioic acid with w = 4, pimelic acid or 1,7-heptanedioic acid with w = 5, suberic acid or 1,8octanedioic 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.
More advantageously, the organogelling compound is sebacic acid or 1,10-decanedioic acid with w = 8.
The diacids can also be dimer diacids 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 Aider for example).
Preferably, a single type of unsaturated fatty acid is dimerized. They derive in particular from the dimerization of an unsaturated fatty acid, in particular in Cx to C34,
FR Text deposited in particular in C12 to C22, in particular in Ci6 to C20, and more particularly in Cig. A preferred fatty acid dimer is obtained by dimerization of linoleic acid, which can then be partially or completely 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. Similarly, fatty acid triacids and fatty acid tetracids can be found, obtained respectively by trimerization and tetramerization of at least one fatty acid.
According to a sixth variant, the organogelling compound is a compound of general formula (VI):
o in which,
- the groups Y and Y ′ represent, independently of one another, an atom or group chosen from: H, - (CH ₂ ) q-CH3, - (CH ₂ ) q-NH2, - (CH ₂ ) q -OH, (CH ₂ ) q-COOH or
O with q an integer varying from 2 to 18, preferably from 2 to 10, preferably from 2 to 4 and p an integer greater than or equal to 2, preferably having a value of 2 or 3.
Among the preferred organogelling compounds corresponding to formula (VI), mention may be made of the following compounds:
FR Text deposit
HN
Y
NH
Ht
O
O
O
HN
O
O
HN
NH
Preferably, according to this variant, the organogelling compound of general formula (VI) is:
HN
According to a seventh variant of this embodiment, the organogelling 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 saturated or unsaturated hydrocarbon chain, linear, branched or cyclic, comprising from 1 to 22 carbon atoms, preferably from 8 to 12 carbon atoms, optionally substituted, and optionally comprising heteroatoms, such as N, O, S, C5-C24 hydrocarbon rings and / or C4-C24 hydrocarbon heterocycles comprising one or more heteroatoms such that N, O, S.
It will not depart from the scope of the invention to combine several different chemical additives such as different organogelling compounds of formula (I), (II), (III), (V), (VI) and (VII), the products of reaction of at least one C3-C12 polyol and at least one C2-C12 aldehyde, in particular those comprising a group of formula (IV), in the oil composition.
FR Text deposit
Advantageously, the coating composition comprises at least one organogelling additive chosen from the compounds of formula (I), the compounds of formula (II) and the compounds of formula (V).
More advantageously, the coating composition comprises at least one organogelling additive chosen from the compounds of formula (I) or the compounds of formula (V).
Preferably, the coating composition comprises at least one organogelling additive which is 2 ', 3-bis [(3- [3, 5-di - / < / 7-butyl-4hy droxy pheny 1] propi ony 1) ] propi onohy drazi de.
Advantageously, the coating composition comprises from 0.1% to 10% by mass, preferably from 0.2% to 5% by mass, more preferably from 0.5% to 3.5% by mass of organogelling chemical additive relative to the total mass of the composition.
Advantageously, the core composition comprises at least one organogelling additive chosen from the compounds of formula (I), the compounds of formula (II) and the compounds of formula (V).
More advantageously, the core composition comprises at least one organogelling additive chosen from the compounds of formula (I) or the compounds of formula (V).
Preferably, the core composition comprises at least one organogelling additive which is sebacic acid.
- Coating composition
The expressions “coating composition” and “coating composition” are used interchangeably in the description.
Advantageously, the coating composition comprises at least one organogelling compound.
More advantageously, the coating composition comprises at least one organogelling compound chosen from the compounds of formula (I), the compounds of formula (II) and the compounds of formula (V). Even more advantageously, the coating composition comprises at least one organogelling compound chosen from the compounds of formula (I) and the compounds of formula (V).
FR Text deposit
Preferably, the coating composition comprises at least one organogelling additive chosen from:
• 2 ’, 3-bis [(3- [3, 5-di- / t77-butyl-4-hydroxyphenyl] propionyl)] propionohydrazide, • sebacic acid, and • mixtures of these compounds.
Advantageously, the coating composition comprises from 0.1% to 10% by mass, preferably from 0.2% to 5% by mass, more preferably from 0.5% to 3.5% by mass of an organogelling compound based on the total mass of the coating composition.
Advantageously, when the organogelling compound is chosen from those corresponding to formula (I), in particular 2 ', 3-bis [(3- [3, 5-di- / t77-butyl-4hydroxyphenyl] propionyl)] propionohydrazide, the coating composition comprises from 0.1% to 5% by mass, preferably from 0.2% to 3.5% by mass of organogelling compound relative to the total mass of the coating composition.
The coating composition comprises the oil, the organogelator compound (s) and, where appropriate, other additives. The other additives can be chosen, for example, from: anti-caking compounds, adhesiveness dopes, elastomers for bitumen, etc.
Advantageously, the coating composition comprises, or is essentially composed of:
80% to 99.9% by mass of at least one oil chosen from: hydrocarbon oils of petroleum origin or of synthesis advantageously from hydrocarbon oils of petroleum origin, • 0.1% to 10% by mass, at least one organogelling compound, • 0% to 10% by mass of one or more other additives, relative to the total mass of the composition.
Preferably, the coating composition comprises, or is essentially composed of:
• 85% to 99.8% by mass of at least one oil, chosen from: hydrocarbon-based oils of petroleum or synthetic origin, advantageously from hydrocarbon-based oils of petroleum origin, • 0.2% to 5% by mass, of at least one organogelling compound,
FR Text deposit • 0% to 10% by mass of one or more other additives, relative to the total mass of the composition.
More preferably, the coating composition comprises, or is essentially composed of:
• 86.5% to 99.5% by mass of at least one oil chosen from: hydrocarbon-based oils of petroleum or synthetic origin, advantageously from hydrocarbon-based oils of petroleum origin, • 0.5% to 3, 5% by mass of at least one organogelling compound, • 0% to 10% by mass of one or more other additives relative to the total mass of the composition.
According to a first preferred embodiment, the organogelling compound is chosen from those corresponding to formula (I), in particular 2 ', 3-bis [(3- [3, 5-di- / ez7butyl-4-hydroxyphenyl] propionyl )] propionohydrazide:
Advantageously according to this embodiment, the coating composition comprises, or is essentially composed of:
• 85% to 99.9% by mass of at least one hydrocarbon-based oil of petroleum origin, • 0.1% to 5% by mass, of at least one organogelling compound of formula (I), advantageously 2 ′ , 3-bis [(3- [3,5-di- / ez7-butyl-4hydroxyphenyl] propionyl)] propionohydrazide, • 0% to 10% by mass of one or more other additives, based on the total mass of the composition.
Preferably, the coating composition comprises, or is essentially composed of:
• 86.5% to 99.8% by mass of at least one hydrocarbon-based oil of petroleum origin, • 0.2% to 3.5% by mass, of at least one organogelling compound of formula (I), advantageously the 2 ′, 3-bis [(3- [3, 5-di- / ez7-butyl-4hy droxy pheny 1] propi ony 1)] propi onohy drazi from, • 0% to 10% by mass of a or several other additives, relative to the total mass of the composition.
FR Text deposit
- Process for preparing the coating composition
The coating compositions can be prepared for example according to the following process comprising the steps of:
a) mixing the oil, for example DAO or RAE oil, and heating to a temperature between 140 and 200 ° C, preferably between 150 and 180 ° C, for example from 1 minute to 30 minutes,
b) adding compound C, mixing and heating to a temperature between 140 and 200 ° C, preferably between 150 and 170 ° C, for example from 10 minutes to 2 hours,
c) optional addition of one or more other additives, mixing and heating to a temperature between 140 and 200 ° C, preferably between 150 and 170 ° C, for example, from 5 minutes to 20 minutes,
d) use in the granule manufacturing process.
The order of steps (a) to (c) can be changed.
- Granules manufacturing process:
Another object 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 coating layer of the core, this process comprising:
i) shaping the core from at least one bitumen base, ii) coating the core over all or part of its surface with a coating composition, iii) optionally, drying the granules obtained with 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, iv) optionally, the coating of the granules resulting from step ii) or from step iii), over all or part of their surface, with at least one anti-caking compound.
Preferably, step ii) of application is done by soaking, spraying, coextrusion, etc.
Preferably, step iv) of coating the granules is done by dusting, sieving, etc.
The shaping of the core of the granules from an optionally additive bitumen base can be carried out according to any known method, for example according to the
FR Manufacturing depot text described in document US 3,026,568, document US 4,279,579, document WO 2009/153324 or document 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 using a drum.
Other techniques can be used in the manufacturing process of the solid bitumen core, in particular molding, pelletizing, extrusion ...
Preferably, the solid bitumen core particles have a longest average dimension ranging from 1 to 30 mm, advantageously from 4 to 20 mm, more advantageously from 4 to 15 mm.
Another object of the invention is a solid bitumen at room temperature in the form of granules capable of being obtained by implementing the method according to the invention as described above. Such a solid bitumen in the form of granules advantageously has the properties described above.
- Uses of solid bitumen granules:
Another object of the invention also relates to the use of solid bitumen granules at room temperature according to the invention as described above as a road binder.
The road binder can be used to manufacture asphalt, in combination with aggregates according to any known process.
Preferably, the bitumen solid at room temperature according to the invention is used for the manufacture of asphalt.
Bituminous mixes are used as materials for the construction and maintenance of road bodies and their coating, as well as for the performance of all road works. Mention may be made, for example, of surface coatings, hot mixes, cold mixes, cold poured mixes, severe emulsions, base, bonding, bonding and surface layers, and other combinations of '' a bituminous binder and road aggregate having particular properties, such as anti-rutting layers, draining asphalt, or asphalts (mixture between a bituminous binder and aggregates of the sand type).
Another object of the invention relates to a process for the manufacture of mixes comprising at least one road binder and aggregates, the road binder being chosen from bitumens according to the invention, this process comprising at least the steps of:
FR Text deposit
- heating the aggregates at a temperature ranging from 100 ° C to 180 ° C, preferably from 120 ° C to 160 ° C,
- mixing of the aggregates with the road binder in a tank such as a kneader or a kneading drum,
- obtaining mixes.
The process of the invention has the advantage of being able to be implemented without prior step of heating the solid bitumen granules.
The process for manufacturing asphalt mixtures according to the invention does not require a step of heating the solid bitumen granules before mixing with the aggregates because, in contact with the hot aggregates, the bitumen solid at room temperature melts.
The bitumen solid at room 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.
Preferably, the step of mixing the aggregates and the road binder is carried out with stirring, then stirring is maintained for at most 5 minutes, preferably at most 1 minute to allow a homogeneous mixture to be obtained.
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 room temperature under optimal conditions, in particular without agglomeration and / or adhesion. 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 of the shearing and it releases the bitumen base. Finally, the presence of the coating layer in the mixture of road binder and aggregates does not degrade the properties of said road bitumen for road application, compared to an uncoated bitumen base.
- Method of transport and / or storage and / or handling of road bitumen
Another object of the invention also relates to a method of transport and / or storage and / or handling of road bitumen, said road bitumen being transported and / or stored and / or handled in the form of solid bitumen granules at ambient temperature. .
FR Text deposit
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 greater than or equal to 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, even more preferably from 40 ° C to 60 ° C .
The bitumen granules according to the invention have the advantage of retaining their divided form, and therefore of being able to be handled, after storage and / or transport at a high ambient temperature. In particular, they have the capacity to flow under their own weight without boiling, which allows them to be stored in packaging in bags, drums or containers of all shapes and all volumes and then transferred from this packaging to equipment, as site equipment (tank, mixer etc ...).
The bitumen granules are preferably transported and / or stored in bulk in bags of 500 g to 100 kg or from 500 kg to 1000 kg commonly called in the field of road bitumen “Big Bag”, said bags being preferably made of hot-melt material. They can also be transported and / or stored in bulk in boxes of 5 kg to 30 kg or in drums of 100 kg to 200 kg.
The different embodiments, variants, preferences and advantages described above for each of the objects of the invention apply to all of the objects of the invention and can be taken separately or in combination.
The invention is illustrated by the following examples given without limitation.
Experimental part :
1. Materials and methods
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 Needle penetration at 25 ° C P25 1/10 mm NF EN 1426 Softening temperatureball and ring TBA ° C NF EN 1427
ICG70130FR Text deposit
The variation of the ball and ring softening temperature (TBA) is measured according to standard NF EN 1427 of said composition between the sample extracted from the upper part of the sample tube and the sample extracted from the lower part of the tube d 'sample.
1.1 Heart composition:
The bitumen base B ₂ is prepared from:
- a bitumen base of grade 35/50, noted Bi, having a P25 penetrability of 34 1/10 mm and a TBA of 52.6 ° C and available commercially from the TOTAL group under the brand AZALT®;
- 1.10 decanoic acid (sebacic acid) noted as acid;
- the flower of sulfur, noted crosslinking;
- zinc octanoate; noted scavenger.
The quantities in percentage by mass used for the bitumen base are indicated in table 2 below.
Table 2
Bitumen b ₂ Bitumen base B ₂ 98.5% Acid 1.5% SB S - Crosslinking Scavenger P25 (1/10 mm) 14 TBA (° C) 93
The bitumen is prepared in the following manner.
For bitumen B ₂ is introduced based bitumen B ₂ in a reactor maintained at 160 ° C with stirring at 300 revolutions / min for two hours. The acid is then introduced into the reactor. The contents of the reactor are kept at 160 ° C. with stirring at 300 rpm for 1 hour.
1.2 Coating composition
Oil: An RAE oil was used, that is to say an aromatic oil, sold by the company TOTAL under the brand Régénis 50®.
FR Text deposit
Organogelator: 2 ', 3-bis [(3- [3,5-di-iert-butyl-4hydroxyphenyl] propionyl)] propionohydrazide (CAS 32687-78-8) sold by the company BASF under the brand Irganox was used MD 1024
The coating composition is prepared according to the following general process:
(i) The oil is heated, for example to 170 ° C;
(ii) 0.9% by mass of organogelling compound is added, relative to the total mass of oil, and mixing is carried out, for example, for 1 hour at 170 ° C. with a stirring speed of 400 rpm;
(iii) When the organogelling additive is completely dissolved, stirring and conditioning are maintained at a temperature at which the solution remains liquid, until used for coating the granules.
2. Preparation of the various granules of solid bitumens Ci
2.1 General method for the preparation of bitumen cores of the granules according to the invention
The bitumen base B ₂ is heated to 160 ° C for two hours in the oven before being poured into a silicone mold having different spherical holes so as to form the hearts of solid bitumen. After having observed the solidification of the bitumen in the mold, the surplus is leveled off with a heated blade with a bunsen burner. After 30 minutes, the solid bitumen in the form of uncoated granules is removed from the mold and stored in a tray covered with silicone paper. The bitumen cores are then left to cool at room temperature for 10 to 15 minutes.
2.2 General method for the preparation of bitumen cores of the granules according to the invention with an industrial process
For the implementation of this method, it is possible to use a device and a method as described in great detail in US Pat. No. 4,279,579. Various models of this device are commercially available from the company Sandwik under the trade name of Rotoform.
Bitumen granules can also be obtained from the bituminous composition B ₂ poured into the tank of such a device and maintained at a temperature between 130 and 160 ° C.
A nozzle or more injection nozzles allows (tent) the transfer of the bitumen composition B ₂ inside the double pastillation drum comprising an external rotary drum, the two drums being equipped with slots, nozzles and orifices allowing the pastillation of bitumen drops through the first
ICG70130FR Text deposit fixed drum and orifices with a diameter between 2 and 8 mm from the rotary external drum. The bitumen drops are deposited on the upper face of a horizontal tread, driven by rollers.
2.3 General method for coating the heart of the granules
The granule cores are soaked in the liquid coating solution and then allowed to dry at room temperature.
FR Text deposit

权利要求:
Claims (15)
[1" id="c-fr-0001]
1. Bitumen solid at room 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:
• an oil chosen from a hydrocarbon oil of petroleum or synthetic origin, • at least one organogelling compound chosen from the compounds of general formula (I), (II) or (V):
Arl-Ri-Ar2 (I) in which:
Arl and Ar2 independently of one another represent a benzene ring or a system of condensed aromatic rings of 6 to 20 carbon atoms, substituted by at least one hydroxyl group, and optionally substituted by one or more C1- alkyl groups C20, and Ri represents an optionally substituted divalent radical, the main chain of which comprises from 6 to 20 carbon atoms and at least one group chosen from amide, ester, hydrazide, urea, carbamate, anhydride functions;
R ₂ - (NH) „CONH- (X) _m - (NHCO) p (NH)„ - R ₂ '(II) in which:
the groups R ₂ and R ₂ ′, which are identical or different, represent a saturated or unsaturated, linear, branched or cyclic hydrocarbon chain, comprising from 1 to 22 carbon atoms, optionally substituted, and optionally comprising one or more heteroatoms such as N, O, S, Cs-C ₂ 4 hydrocarbon rings and / or C4-C ₂ 4 hydrocarbon heterocycles comprising one or more heteroatoms such as N, O, S, and R ₂ 'may be H;
FR Text deposited the group X represents a hydrocarbon chain, saturated or unsaturated, linear, cyclic or branched, comprising from 1 to 22 carbon atoms, optionally substituted, and optionally comprising one or more heteroatoms such as N, O, S, rings C5-C24 hydrocarbons and / or C4-C24 hydrocarbon heterocycles comprising one or more heteroatoms such as N, O, S;
n, m and p are integers having a value of 0 or 1 independently of each other;
R ₅ - (COOH) _z (V) in which:
R5 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 varying from 2 to 4.
[2" id="c-fr-0002]
2. Bitumen according to claim 1, in which the hydrocarbon oil is chosen from hydrocarbon oils of petroleum origin.
[3" id="c-fr-0003]
3. Bitumen according to any one of the preceding claims in which the hydrocarbon oil is chosen from aromatic oils having a content of aromatic compounds between 30 and 95% by mass, advantageously between 50 and 95% by mass, more advantageously between 60 and 95% by mass relative to the total mass of the aromatic oil.
[4" id="c-fr-0004]
4. Bitumen according to any one of claims 1 and 2 in which the hydrocarbon oil is chosen from paraffinic oils having a total content of paraffinic compounds of at least 50% by mass relative to the total mass of the paraffinic oil.
[5" id="c-fr-0005]
5. Bitumen according to claim 4, in which the paraffinic oil has the respective contents:
(i) a total content of paraffinic compounds of between 50% and 90%;
(ii) a total content of naphthenic compounds of between 5% and 25%; and
FR Text deposit (iii) a total content of aromatic compounds between 5% and 25%, the percentages being expressed by mass relative to the total mass of the paraffinic oil.
[6" id="c-fr-0006]
6. Bitumen according to any one of the preceding claims, in which the coating layer comprises from 80% to 99.9% of at least one oil, by mass relative to the total mass of the coating layer.
[7" id="c-fr-0007]
7. Bitumen according to any one of the preceding claims, in which the coating layer comprises from 0.1 to 10%, preferably from 0.2% to 5% by mass, more preferably from 0.5% to 3.5 % by mass of organogelling compound relative to the total mass of the coating layer.
[8" id="c-fr-0008]
8. Bitumen according to any one of the preceding claims, in which the core also comprises at least one compound chosen from organogelling compounds.
[9" id="c-fr-0009]
9. Bitumen according to any one of the preceding claims, in which the core further comprises at least one pitch having a penetrability at 25 ° C ranging from 0 to 20 1/10 mm, a softening temperature of ball and rings (TBA) ranging from 115 ° C to 175 ° C, it being understood that the penetrability is measured according to standard EN 1426 and that the TBA is measured according to standard EN 1427.
[10" id="c-fr-0010]
10. A method of manufacturing a bitumen according to any one of claims 1 to 9, this method comprising:
i) forming the core from at least one bitumen base, ii) coating the core over all or part of its surface with a coating composition, iii) optionally, drying the granules obtained with 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.
FR Text deposit
[11" id="c-fr-0011]
11. Bituminous mix which comprises a bitumen according to any one of claims 1 to 9 and which further comprises aggregates and optionally mineral and / or synthetic fillers.
[12" id="c-fr-0012]
12. Bituminous mix according to claim 11 which is a road mix, bituminous concrete, or bituminous mastic.
[13" id="c-fr-0013]
13. Process for the manufacture of mixes comprising at least one road binder and aggregates, the road binder being chosen from bitumens according to any one of claims 1 to 9, 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 of the aggregates with the road binder in a tank such as a kneader or a kneading drum,
- obtaining mixes.
[14" id="c-fr-0014]
14. The method of claim 13, which does not include a step of heating the road binder before it is mixed with the aggregates.
[15" id="c-fr-0015]
15. Method for transporting and / or storing bitumen, said bitumen being transported and / or stored in the form of solid bitumen at room temperature according to any one of claims 1 to 9.

类似技术:

---

公开号 | 公开日 | 专利标题

---

FR3059674A1|2018-06-08|SOLID BITUMEN AT AMBIENT TEMPERATURE

---

EP3307830B1|2020-03-18|Bitumen that is solid at ambient temperature

---

EP3174925A1|2017-06-07|Road bitumen granules

---

CA2956868A1|2016-02-04|Method for the transportation and/or storage of road bitumen

---

EP3510105B1|2021-07-21|Bitumenous composition for high-modulus coated material

---

FR3055568A1|2018-03-09|METHOD FOR MANUFACTURING PELLET MATERIAL FOR USE AS A ROAD BINDER OR SEALING BINDER AND DEVICE FOR MANUFACTURING THE SAME

---

FR3061190A1|2018-06-29|SOLID BINDER AT AMBIENT TEMPERATURE

---

FR3065464A1|2018-10-26|SOLID BITUMEN AT AMBIENT TEMPERATURE

---

EP3510104B1|2021-07-28|Solide bitumeat room temperature

---

FR3065465B1|2019-06-28|SOLID BITUMEN AT AMBIENT TEMPERATURE

---

FR3059673A1|2018-06-08|SOLID BINDERS

---

FR3061191A1|2018-06-29|COLOR ASPHALT COMPOSITION FOR REALIZING COATINGS

---

WO2017203154A1|2017-11-30|Bitumen which is solid at ambient temperature

---

OA19100A|2020-01-20|Solid bitumen at room temperature.

---

FR3065462B1|2019-06-28|PROCESS FOR THE PREPARATION OF SOLID BITUMEN AT AMBIENT TEMPERATURE IN A FLUIDIZED AIR BED

---

FR3044675A1|2017-06-09|THERMORETICULATED BITUMEN-POLYMER COMPOSITION AND PROCESS FOR PREPARING THE SAME

---

OA19552A|2020-12-11|Bituminous composition for high modulus Mixes.

---

OA19195A|2020-03-09|Solid binders

---

OA19430A|2020-09-18|Bitumen solid at room temperature.

---

EP3894469A1|2021-10-20|Bitumen granules which are solid at ambient temperature

---

FR3059672A1|2018-06-08|SOLID OIL COMPOSITIONS

---

OA19547A|2020-12-11|A method of transporting and / or storing road bitumen.

---

FR3055623A1|2018-03-09|COLD SOLID CLEAR BINDER

---

FR3044674A1|2017-06-09|NON-RETICULATED BITUMEN-POLYMER COMPOSITION AND PROCESS FOR PREPARING THE SAME

同族专利:

---

公开号 | 公开日

---

FR3059674B1|2018-11-23|

---

WO2018104660A1|2018-06-14|

---

US20190330472A1|2019-10-31|

---

EP3551700A1|2019-10-16|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

FR2992654A1|2012-07-02|2014-01-03|Total Raffinage Marketing|BITUMINOUS COMPOSITIONS ADDITIVE TO IMPROVED THERMOREVERSIBLE PROPERTIES|WO2020120408A1|2018-12-12|2020-06-18|Total Marketing Services|Bitumen granules which are solid at ambient temperature|

---

WO2020120407A1|2018-12-12|2020-06-18|Total Marketing Services|Bitumen which is solid at ambient temperature|US3026568A|1958-11-14|1962-03-27|Schuller Services Ltd|Method for producing coated bitumen pellets|

---

EP0012192B1|1978-12-08|1983-01-12|Santrade Ltd.|Device for extruding fluid masses from a container|

---

US4305812A|1980-06-19|1981-12-15|Mobil Oil Corporation|Solvent deasphalting by polarity gradient extraction|

---

US4455216A|1980-12-04|1984-06-19|Mobil Oil Corporation|Polarity gradient extraction method|

---

WO2002044307A1|2000-11-30|2002-06-06|Jgc Corporation|Method of refining petroleum|

---

DE10239423A1|2002-08-28|2004-03-11|Degussa Ag|Silica|

---

WO2007058994A2|2005-11-14|2007-05-24|Kraton Polymers Research B.V.|Process for preparing a bituminous binder composition|

---

DE102006020987A1|2006-05-04|2007-11-08|Degussa Gmbh|Dispersion of fumed silica|

---

DE102006039273A1|2006-08-22|2008-02-28|Evonik Degussa Gmbh|Pyrogenic silica for use as adjuvant in pharmaceutical and cosmetic compositions|

---

DE102006048508A1|2006-10-13|2008-04-17|Evonik Degussa Gmbh|Surface-modified silicic acids|

---

JP5325207B2|2007-05-01|2013-10-23|クレイトン・ポリマーズ・ユー・エス・エル・エル・シー|Bitumen binder composition and method for preparing the same|

---

DE102007024094A1|2007-05-22|2008-11-27|Evonik Degussa Gmbh|Hydrophobic fumed silica and silicone rubber compositions containing the fumed silica|

---

DE102007024100A1|2007-05-22|2008-11-27|Evonik Degussa Gmbh|Pyrogenated silanized and ground silicic acid|

---

DE102007035955A1|2007-07-30|2009-02-05|Evonik Degussa Gmbh|Surface-modified, pyrogenic silicas|

---

EP2067826B1|2007-12-05|2014-02-12|Evonik Degussa GmbH|Procédé pour la modification structurale de silices|

---

US20110115116A1|2008-06-20|2011-05-19|De Amorim Novais Da Costa Nobrega Joao Miguel|Method for preparing coated binder units|

---

US20110233105A1|2008-08-29|2011-09-29|Billian I.P. Limited|Asphalt pellets|

---

US8038971B2|2008-09-05|2011-10-18|Cabot Corporation|Fumed silica of controlled aggregate size and processes for manufacturing the same|

---

HUE031263T2|2009-07-03|2017-07-28|Evonik Degussa Gmbh|Hydrophilic silica as filler for silicone rubber formulations|

---

FR2948677B1|2009-07-29|2011-09-16|Total Raffinage Marketing|PROCESS FOR THE PREPARATION OF BITUMEN / POLYMERIC COMPOSITIONS RETICULATED WITHOUT RETICULATING AGENT|

---

CN103597035B|2011-06-07|2016-03-16|国际壳牌研究有限公司|Prepare the method for coating and bonding agent unit|

---

FR3014111B1|2013-12-03|2015-12-25|IFP Energies Nouvelles|METHOD FOR REFINING A HEAVY HYDROCARBON LOAD USING SELECTIVE CASCADE DEASPHALTATION|

---

FR3024456B1|2014-08-01|2016-08-19|Total Marketing Services|BITUMEN GRANULES|FR3085170B1|2018-08-22|2021-06-04|Total Marketing Services|THERMOREVERSIBLE BITUMINOUS COMPOSITION|

---

FR3085168B1|2018-08-22|2020-09-18|Total Marketing Services|THERMOREVERSIBLE BITUMINOUS COMPOSITION|

---

FR3085169B1|2018-08-22|2020-09-18|Total Marketing Services|THERMOREVERSIBLE BITUMINOUS COMPOSITION|

---

WO2020120314A1|2018-12-10|2020-06-18|Total Marketing Services|Bituminous composition solid at ambient temperature|

---

CA3130924A1|2019-03-18|2020-09-24|Regis Vincent|Bituminous composition solid at ambient temperature|

---

CN111647277A|2020-05-19|2020-09-11|中国森田企业集团有限公司|Solid pellets for transporting asphalt in solidified form|

法律状态:
2017-11-20| PLFP| Fee payment|Year of fee payment: 2 |

---

2018-06-08| PLSC| Publication of the preliminary search report|Effective date: 20180608 |

---

2019-11-20| PLFP| Fee payment|Year of fee payment: 4 |

---

2020-11-20| PLFP| Fee payment|Year of fee payment: 5 |

---

2021-12-24| PLFP| Fee payment|Year of fee payment: 6 |

优先权:

---

申请号 | 申请日 | 专利标题

---

FR1662031|2016-12-07|

---

FR1662031A|FR3059674B1|2016-12-07|2016-12-07|SOLID BITUMEN AT AMBIENT TEMPERATURE|FR1662031A| FR3059674B1|2016-12-07|2016-12-07|SOLID BITUMEN AT AMBIENT TEMPERATURE|

---

EP17816996.7A| EP3551700A1|2016-12-07|2017-12-06|Bitumen solid at ambient temperature|

---

US16/465,170| US20190330472A1|2016-12-07|2017-12-06|Bitumen solid at ambient temperature|

---

PCT/FR2017/053413| WO2018104660A1|2016-12-07|2017-12-06|Bitumen solid at ambient temperature|