WO2023057723A1 - Compositions bitumineuses modifiees par incorporation d'hydroxyde alcalin et piegeant du co2, procedes et utilisations associes - Google Patents
Compositions bitumineuses modifiees par incorporation d'hydroxyde alcalin et piegeant du co2, procedes et utilisations associes Download PDFInfo
- Publication number
- WO2023057723A1 WO2023057723A1 PCT/FR2022/051884 FR2022051884W WO2023057723A1 WO 2023057723 A1 WO2023057723 A1 WO 2023057723A1 FR 2022051884 W FR2022051884 W FR 2022051884W WO 2023057723 A1 WO2023057723 A1 WO 2023057723A1
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- WIPO (PCT)
- Prior art keywords
- mass
- bituminous composition
- bituminous
- bitumen base
- bitumen
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 357
- 238000000034 method Methods 0.000 title claims abstract description 44
- 150000008044 alkali metal hydroxides Chemical class 0.000 title claims abstract description 38
- 238000010348 incorporation Methods 0.000 title claims abstract description 38
- 239000010426 asphalt Substances 0.000 claims abstract description 180
- 239000002585 base Substances 0.000 claims abstract description 117
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 122
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 37
- 239000002318 adhesion promoter Substances 0.000 claims description 32
- -1 alkyl amido amines Chemical class 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 claims description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- 229920001971 elastomer Polymers 0.000 claims description 25
- 239000000806 elastomer Substances 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 20
- 239000007795 chemical reaction product Substances 0.000 claims description 16
- 230000006641 stabilisation Effects 0.000 claims description 15
- 238000011105 stabilization Methods 0.000 claims description 15
- 239000000945 filler Substances 0.000 claims description 14
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 14
- 239000011707 mineral Substances 0.000 claims description 14
- 235000010755 mineral Nutrition 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 13
- 150000004985 diamines Chemical class 0.000 claims description 12
- 229920000768 polyamine Polymers 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 10
- 150000002462 imidazolines Chemical class 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
- 238000003801 milling Methods 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 4
- 239000012764 mineral filler Substances 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 238000005185 salting out Methods 0.000 claims description 2
- 238000004078 waterproofing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 description 20
- 239000012071 phase Substances 0.000 description 19
- 239000000654 additive Substances 0.000 description 18
- 230000032683 aging Effects 0.000 description 15
- 239000011734 sodium Substances 0.000 description 13
- 239000011230 binding agent Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 9
- 238000003860 storage Methods 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- 239000003570 air Substances 0.000 description 6
- 229920001400 block copolymer Polymers 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241001307210 Pene Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000003784 tall oil Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004525 petroleum distillation Methods 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2555/00—Characteristics of bituminous mixtures
- C08L2555/30—Environmental or health characteristics, e.g. energy consumption, recycling or safety issues
- C08L2555/32—Environmental burden or human safety, e.g. CO2 footprint, fuming or leaching
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2555/00—Characteristics of bituminous mixtures
- C08L2555/40—Mixtures based upon bitumen or asphalt containing functional additives
- C08L2555/50—Inorganic non-macromolecular ingredients
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
Definitions
- the present invention relates to the technical field of bitumens. More precisely, it relates to bituminous compositions making it possible to trap CO 2 , and, consequently, offering the possibility of reducing the quantities of CO 2 emitted into the atmosphere.
- the invention also relates to the processes for preparing such compositions, as well as their uses in the road sector and in the industrial sector.
- CO 2 is a greenhouse gas.
- the emission of CO 2 into the atmosphere contributes to global warming.
- solutions are sought to reduce the quantity of CO 2 released into the atmosphere.
- Means for capturing the CO 2 produced by various human activities are therefore of great interest.
- the applicant proposes new bituminous compositions making it possible to store CO 2 in a sustainable manner, processes for obtaining such compositions and their use in the road and industrial fields.
- the invention relates to a bituminous composition
- a bituminous composition comprising a bitumen base modified by incorporating an alkali metal hydroxide, the bitumen base representing at least 72% by mass of the said bituminous composition, characterized in that CO 2 is trapped in the said bituminous composition and represents from 0.5 to 5% by mass, preferably from 0.5 to 4% by mass, and preferably from 0.5 to 3% by mass, and even more preferably from 0.5 to 2% or even from 0.5 to 1.5% or even from 0.7 to 2% by mass, of the mass of bitumen base and the mass of the bituminous composition is stable at 25° C. and under 1013.25 hPa, over a period Ps of at least 10 hours, preferably of at least 15 hours.
- the mass of the bituminous composition is considered to be stable over a given period, in particular over a period Ps of 10 hours to 100 hours, in particular from 19 to 91 hours, and typically 19 hours, if this mass does not decrease. more than 2%, preferably if this mass does not decrease by more than 1%, and preferably does not decrease by more than 0.5%, and even more preferably does not decrease by more than 0.05% compared to the initial mass of the composition, i.e. its mass at the beginning of the period considered.
- the stability of a composition as it is at a given instant t can therefore be evaluated, by measuring the mass of the latter at this instant t, then at this instant t+19 hours typically, or more generally t + the period Ps evaluation period.
- the stability of the mass of the bituminous composition is evaluated, leaving a bituminous composition, at 25° C. and under atmospheric pressure (that is to say under a pressure of 1013 .25 hPa). Under these conditions, the atmosphere in which the bituminous composition is located has no influence. However, typically, stability is evaluated in ambient air. In the context of the invention, it was found that when an alkali metal hydroxide had been incorporated into a bitumen base, it was then possible to incorporate CO 2 into the matrix obtained formed from the mixture bitumen/alkali metal hydroxide base and, without a total release of the incorporated CO 2 then taking place.
- the stability of the mass of the bituminous composition reflects the fact that the quantity of CO 2 trapped in said composition is stabilized.
- the inventors have demonstrated, in the context of the invention, that this stabilization occurs while a significant part of the mass of CO 2 initially incorporated is still trapped within the bituminous composition. In the context of the invention, reference is made indiscriminately to trapped CO 2 or incorporated CO 2 .
- bituminous compositions are obtained by directly introducing gaseous CO 2 into the bitumen base modified by incorporating an alkali metal hydroxide.
- gaseous CO 2 into the bitumen base modified by incorporating an alkali metal hydroxide.
- alkaline hydroxide see other additives as explained below
- the CO 2 was trapped in the bituminous composition, following a trapping step, in particular carried out by placing said bitumen base modified by incorporating an alkali hydroxide, in a chamber under CO 2 pressure, followed by a step of releasing part of the trapped CO 2 , until the mass of the bituminous composition obtained stabilizes, this stabilization occurring in particular 3 hours or more after the end of the trapping step, in particular 5 to 10 hours after the end of the trapping step.
- a trapping step in particular carried out by placing said bitumen base modified by incorporating an alkali hydroxide, in a chamber under CO 2 pressure, followed by a step of releasing part of the trapped CO 2 , until the mass of the bituminous composition obtained stabilizes, this stabilization occurring in particular 3 hours or more after the end of the trapping step, in particular 5 to 10 hours after the end of the trapping step.
- the incorporation of CO 2 during this trapping step is carried out by placing the modified bitumen base in a chamber under CO 2 pressure, the chamber being maintained at a temperature ranging from 10 to 200° C., preferably ranging from 20 to 160° C., and preferably ranging from 25 to 160° C., or even 80 to 160° C., the CO 2 pressure being in particular chosen in the range ranging from 5.10 3 to 8.10 4 hPa , preferably in the range going from 5.10 3 to 5.10 4 hPa, and preferentially in the range going from 1.10 4 to 3.10 4 hPa.
- bituminous compositions comprising a bitumen base in which an alkali metal hydroxide has been incorporated have a mass which is stable at 25° C. and under 1013.25 hPa, over a period Ps of at least 10 a.m., preferably at least 3 p.m., and typically 7 p.m.
- the mass of the composition does not decrease by more than 2%, preferably does not decrease not more than 1%, and preferably does not decrease by more than 0.5%, and even more preferably does not decrease by more than 0.05% relative to the initial mass of the composition, at the start of the period Ps considered.
- a bituminous composition according to the invention has a stable mass, whereas it has a quantity of CO 2 which has been incorporated into the bituminous composition and which remains trapped in said bituminous composition.
- This quantity of CO 2 which can be described as stabilized, represents from 0.5 to 5% by mass, preferably 0.5 to 4% by mass of the mass of the bitumen base, and preferentially from 0.5 to 3 % by mass of the mass of the bitumen base, and even more preferably from 0.5 to 2% by mass or else from 0.5 to 1.5% by mass or even from 0.7 to 2% by mass , of the mass of the bitumen base present in the bituminous composition.
- the amount of CO2 can be determined by weighing.
- the masses can be determined by weighing, with a precision balance, in particular to within 0.0001 g (for example Balance Sartorius Practum 224-1 S).
- the weighings are carried out at 25°C and under atmospheric pressure (1013.25 hPa).
- the bituminous compositions according to the invention are obtained by placing an original bituminous composition (also called modified bitumen base) under CO2 pressure.
- the original bituminous composition comprises all the components of the desired bituminous composition, therefore in particular the alkaline hydroxide, with the exception of CO 2 .
- the incorporation of CO 2 is carried out by placing such an original bituminous composition in a chamber under CO 2 pressure, the chamber being maintained at a temperature ranging from 10 to 200° C., preferably ranging from 20 at 160° C., and preferably ranging from 25 to 160° C., or even 80 to 160° C., the CO 2 pressure being in particular chosen in the range ranging from 5.10 3 to 8.10 4 hPa (equivalent to 5-80 bars), preferably in the range going from 5.10 3 to 5.10 4 hPa, and preferentially in the range going from 1.10 4 to 3.10 4 hPa.
- the mass of CO 2 incorporated into a bituminous composition corresponds to the difference between the mass of said bituminous composition and the mass of the same original bituminous composition.
- the mass of CO 2 incorporated can be monitored over time, by following the mass of the bituminous composition.
- the end of the CO 2 trapping step in particular if the trapping is carried out until the composition is saturated with CO 2 , when the bituminous composition obtained comprising trapped CO 2 is then stored at 25° C. and under atmospheric pressure, there is first of all a phase of release of part of the incorporated CO 2 , which results in a loss of mass of the composition.
- This stabilization of the CO 2 incorporated in the bituminous composition takes the form of a stabilization of the mass of the bituminous composition. It is, in particular, these stabilized bituminous compositions which form the subject of the invention.
- these stabilized bituminous compositions which form the subject of the invention.
- there is question of CO 2 trapped but within the composition the CO 2 trapped, or at least part of the CO 2 trapped, may not be in the CO 2 form, but have reacted with one of the components present or incorporated in the bituminous composition, and in particular be in the form of one or more reaction products with the alkaline hydroxide.
- the period Ps over which the mass of the bituminous composition according to the invention is stable starts, after a release phase Pr, during which part of the trapped CO2 is released from the bituminous composition.
- This release phase Pr is most often 5 to 10 hours, and typically 5 hours, after the end of the CO 2 trapping step.
- the end of the CO 2 trapping step corresponds, in particular, to the moment when the bituminous composition is no longer under a CO 2 pressure.
- the bituminous composition can be placed at 25° C. and under 1013.25 hPa.
- bituminous composition it is also possible for the bituminous composition to be subjected to heating during this Pr release phase, which will have the effect of accelerating the release of part of the CO 2 and therefore of reducing the duration of the release phase.
- Pr release phase Once the Pr release phase is complete, the remaining CO 2 remains trapped within the bituminous composition, under so-called standard storage conditions (at 25°C and under 1013.25 hPa), which results in stabilization of the mass of the bituminous composition.
- the mass of the bituminous composition is understood as the mass of all the components present (in particular the bitumen base, the alkaline hydroxide introduced, and the other components possibly present) but also of the CO 2 trapped in the bituminous composition when the mass of it is measured.
- the invention proposes both compositions which allow sufficient storage of CO 2 to be of interest in the fight against the greenhouse effect and global warming and which are satisfactory, in terms of performance, to respond requirements, in particular stability to operating stresses, in the fields of road and industrial applications.
- the bitumen base has been modified by incorporating 0.1 to 9% by mass, preferably 0.2 to 4.5% by mass, and preferentially 0.2 to 2 % by mass of alkaline hydroxide, relative to the mass of bitumen base.
- the CO 2 is found, at least in part, in the bituminous composition in the form of one or more reaction product(s) with the alkali metal hydroxide.
- the alkaline hydroxide is NaOH or KOH.
- the alkaline hydroxide is NaOH
- at least part of the incorporated NaOH, or even all of the incorporated NaOH can react with the trapped CO 2 and will be found, in the bituminous composition, in the form of a or more reaction products between CO 2 and NaOH, in particular in the form of NaHCO 3 and Na 2 CO 3 , or exclusively in the form of NaHCO 3 .
- the alkaline hydroxide is KOH
- at least part of the incorporated KOH, or even all of the incorporated KOH may react with the trapped CO 2 and will be found, in the bituminous composition, in the form of one or more reaction products between CO 2 and KOH, in particular in the form of KHCO 3 and of K 2 CO 3 , or exclusively in the form of KHCO 3 .
- the invention relates to a method for preparing a bituminous composition comprising a bitumen base representing at least 72% by weight of said bituminous composition, said process comprising the following successive steps: a) obtaining a modified bitumen base, comprising the incorporation of an alkaline hydroxide into a bitumen base, said incorporation being followed or accompanied by a mixture, preferably under heating at a temperature belonging to the range going from 90 to 230°C, preferably to the range going from 120 to 200°C, and preferentially to the range going from 120 to 180°C, b ) trapping of CO2 in the modified bitumen base at a mass content representing, in particular, from 0.8 to 5.8% by mass, preferably from 0.8 to 4.5% by mass, preferably from 0.8 to 3.5 % by mass, and even more preferably from 0.8 to 2.6% by mass, or else from 0.8 to 1.8% by mass of the mass of the bitumen base.
- a subject of the invention is also a method for preparing a bituminous composition
- a method for preparing a bituminous composition comprising the following successive steps: a) obtaining a modified bitumen base, comprising the incorporation of an alkali metal hydroxide into a bitumen base, said incorporation being followed or accompanied by mixing, preferably under heating at a temperature belonging to the range from 90 to 230°C, preferably to the range from 120 to 200°C, and preferentially to the range from 120 to 180° C., b) trapping of CO2 in the modified bitumen base until saturation with CO2.
- the incorporation of CO 2 is carried out by placing the modified bitumen base, in a chamber under CO2 pressure, the chamber being maintained at a temperature ranging from 10 to 200 ° C, preferably ranging from 20 to 160° C., and preferably ranging from 25 to 160° C., or even 80 to 160° C., the CO 2 pressure being in particular chosen in the range ranging from 5.10 3 to 8.10 4 hPa, preferably in the range going from 5.10 3 to 5.10 4 hPa, and preferentially in the range going from 1.10 4 to 3.10 4 hPa.
- the mass of alkali metal hydroxide incorporated represents from 0.1 to 9% by mass, preferably from 0.2 to 4.5 %, and preferably from 0.2 to 2% by mass, of the bitumen base mass.
- the alkaline hydroxide is preferably NaOH or KOH.
- an adhesion promoter chosen from amines, diamines, polyamines, alkyl amido amines, amidopolyamines, imidazolines, and their mixtures, is also incorporated into the bitumen base, said adhesion promoter being preferably introduced in a proportion of 0.01 to 2.5% by mass, preferentially from 0.05 to 1.1% by mass, and even more preferably from 0.1 to 0.4% by mass, of the total mass of the bitumen base.
- one or more polymers chosen from olefinic polymers and elastomers, in particular from crosslinkable elastomers is (are) also incorporated ( s) in the bitumen base, the said polymer(s) preferably being introduced at a rate of preferably from 0.1 to 12% by mass, preferably from 0.3 to 10%, and preferably from 0.5 to 7% by mass, of the mass of the bitumen base.
- the methods according to the invention may comprise a step of releasing part of the trapped CO2, from the bituminous composition resulting from step b), at the end of which the mass of the bituminous composition is stable.
- said salting-out step results in a quantity of CO 2 trapped in the bituminous composition, corresponding to 0.5 to 5% by mass, preferably to 0.5 to 4% by mass, and preferentially to 0 .5 to 3% by mass, and even more preferably at 0.5 to 2% or even at 0.5 to 1.5% or even at 0.7 to 2% by mass, relative to the mass of the bitumen base.
- the invention also relates to the bituminous compositions that can be obtained, according to the methods of the invention, and this regardless of their variant embodiment.
- the invention relates to bituminous compositions comprising a bitumen base and one or more reaction products of CO 2 with an alkali metal hydroxide, in particular chosen from NaOH and KOH.
- the invention relates to bituminous compositions comprising one or more reaction products of CO 2 with NaOH.
- such compositions comprise NaHCOs, or even NaHCOs and Na 2 CO 3 , as reaction product(s) of CO 2 with NaOH.
- the invention relates to bituminous compositions comprising from 2 to 210 mmoles (millimoles) of NaHCO 3 and of Na 2 CO 3 , per 100 g of bituminous composition, preferably from 5 to 80 mmoles of NaHCO 3 and of Na 2 CO 3 , per 100 g of bituminous composition, and even more preferably from 5 to 40 mmoles of NaHCO 3 and of Na 2 CO 3 , per 100 g of bituminous composition.
- the invention also relates to bituminous compositions comprising from 2 to 210 mmoles (millimoles) of Na 2 CO 3 , per 100 g of bituminous composition, preferably from 5 to 80 mmoles of Na 2 CO 3 , per 100 g of composition bituminous, and even more preferably from 5 to 40 mmoles of Na 2 CO 3 , per 100 g of bituminous composition.
- the invention also relates to bituminous compositions comprising one or more reaction products of CO 2 with KOH.
- such compositions comprise KHCO 3 , or even KHCO 3 and K 2 CO 3 , as reaction product(s) of CO 2 with KOH.
- the invention relates to bituminous compositions comprising from 2 to 145 mmol (millimoles) of KHCO 3 and of K 2 CO 3 , per 100 g of bituminous composition, preferably from 3 to 53 mmol of KHCO 3 and of K 2 CO 3 , per 100 g of bituminous composition, and even more preferably from 3 to 27 mmoles of KHCO 3 and of K 2 CO 3 , per 100 g of bituminous composition.
- the invention also relates to bituminous compositions comprising from 2 to 145 mmoles (millimoles) of K 2 CO 3 , per 100 g of bituminous composition, preferably from 3 to 53 mmoles of K 2 CO 3 , per 100 g of composition bituminous, and even more preferably from 3 to 27 mmoles of K 2 CO 3 , per 100 g of bituminous composition.
- bitumen base represents at least 72% by mass, preferably at least 83% by mass and preferably at least 89% by mass of the total mass. of the bituminous composition.
- bituminous compositions according to the invention do not include bituminous emulsions. Indeed, in bituminous emulsions, the amount of bitumen base is much smaller, due to the presence of an aqueous phase.
- a composition according to the invention further comprises an adhesion promoter chosen from amines, diamines, polyamines, alkyl amido amines, amidopolyamines, imidazolines, and their mixtures, said adhesion promoter preferably representing 0.01 to 2.5% by mass, preferentially 0.05 to 1.1% by mass, and even more preferably 0.1 to 0.4% by mass, the mass of the bitumen base.
- an adhesion promoter chosen from amines, diamines, polyamines, alkyl amido amines, amidopolyamines, imidazolines, and their mixtures, said adhesion promoter preferably representing 0.01 to 2.5% by mass, preferentially 0.05 to 1.1% by mass, and even more preferably 0.1 to 0.4% by mass, the mass of the bitumen base.
- a composition according to the invention further comprises one or more polymers chosen from olefinic polymers and elastomers, in particular from crosslinked or crosslinkable elastomers. , preferably representing from 0.1 to 12% by mass, preferably from 0.3 to 10% by mass, and even more preferably from 0.5 to 7% by mass, of the mass of the bitumen base.
- bituminous compositions according to the invention find different applications. Also, the invention also relates to:
- bituminous composition according to the invention, to prepare a sealing coating, a membrane or an impregnation layer; as well as the processes for preparing such a sealing coating, such a membrane or such an impregnation layer;
- bituminous binders comprising a bituminous composition according to the invention
- bituminous composition according to the invention as a bituminous binder in a bituminous mix comprising a bituminous composition according to the invention, aggregates, and optionally mineral and/or synthetic fillers; as well as the methods for preparing such a bituminous mix;
- bituminous composition according to the invention as a bituminous binder in an asphalt comprising a bituminous composition according to the invention, and mineral and/or synthetic fillers; as well as the processes for preparing such an asphalt;
- bituminous composition according to the invention as a bituminous binder in a surface dressing, a hot mix, a cold mix, a cold poured mix, a grave emulsion or a wearing course , which comprises a bituminous composition according to the invention aggregates and/or recycling millings; as well as the methods for preparing such a surface coating, hot mix, cold mix, cold mix, such a serious emulsion or wearing course.
- the invention relates to a method for preparing an asphalt characterized in that it comprises the hot mixing of a bituminous composition according to the invention or capable of being obtained according to a method according to the invention, with mineral and/or synthetic fillers.
- hot mixing with the bituminous composition can be carried out at a temperature of 80 to 200°C, preferably of 80 to 180°C and preferentially of 100 to 160°C.
- the invention also relates to the use of an alkali metal hydroxide in a bituminous composition in which CO 2 is incorporated, to obtain stabilization of the quantity of CO 2 remaining trapped within said bituminous composition.
- bitumen compositions modified by adding at least one additive or adjuvant, also called bituminous compositions. These may comprise one or more bitumens.
- the bitumen(s) present in the bituminous compositions according to the invention are called "bitumen base" and constitute(s) a major content of the composition, that is to say represent(s) at least 72% by mass, of the total mass of the bituminous composition, and preferably at least 83%, even at least 89% and even at least 95% by mass of the total mass of the bituminous composition.
- bitumen or bitumens used are advantageously chosen from bitumens originating from the refining of crude oil, in particular bitumens containing asphaltenes or pitches.
- the bitumens can be obtained by conventional processes for the manufacture of bitumens in refineries, in particular by direct distillation and/or distillation vacuum oil. These bitumens can optionally be visbroken and/or deasphalted and/or air-rectified.
- bituminous compositions In the conventional methods for manufacturing bituminous compositions, the process is carried out at manufacturing temperatures of between 90° C. and 230° C., preferably between 120° C. and 200° 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.
- manufacturing temperature is meant the heating temperature of the bitumen(s) before mixing with the additives, as well as the mixing temperature.
- the heating temperature and duration vary according to the quantity of bitumen used and are defined by standard NF EN 12594.
- Blown bitumens can be produced in a blowing unit, by passing a flow of air and/or oxygen through a starting bitumen or mixture of bitumens.
- This operation can be carried out in the presence of an oxidation catalyst, for example phosphoric acid.
- an oxidation catalyst for example phosphoric acid.
- the blowing is carried out at high temperatures, of the order of 200 to 300° C., for relatively long durations typically comprised between 30 minutes and 2 hours, continuously 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.
- bitumens can be hard grade bitumens (such as grades 10/20 and 20/30) or soft grade (such as grade 160/220) defined by standard EN 12591.
- bitumen base consists of a hard grade bitumen or a mixture of hard grade bitumens, in particular chosen from among 35/50 grade bitumens. , 20/30 and 10/20.
- the bitumen bases that can be used in the context of the invention preferably have a penetrability, measured at 25° C. according to standard EN 1426, of 5 to 330 1/10 mm, preferably between 10 to 220 1/ 10 mm, more preferably from 10 to 120 1/10 mm.
- a penetrability measured at 25° C. according to standard EN 1426
- the so-called “needle penetrability” measurement is carried out by means of a standardized test NF EN 1426 at 25° C. (Pene). This penetrability characteristic is expressed in tenths of a millimeter (dmm or 1/10 mm). Needle penetrability, measured at 25°C, according to the standardized test NF EN 1426, represents the measurement of the penetration into a sample of bitumen, after a time of 5 seconds, of a needle whose weight with its support is 100 g.
- alkali metal hydroxide By way of example of alkali metal hydroxide, mention may be made of NaOH, KOH, Mg(OH) 2 , Ca(OH) 2 or else Li(OH) 2 .
- the alkaline hydroxide can be introduced into the bitumen composition in the form of a suspension or a solution in a solvent (in particular water or ethanol), but is preferably directly introduced under the form of a powder or of a set of particles, in particular of an anhydrous alkali metal hydroxide.
- the alkaline hydroxide used, and in particular the NaOH or KOH used forms particles whose maximum particle size is equal to or less than 100 ⁇ m, and preferably whose maximum particle size is equal to or less than 60 ⁇ m.
- the average maximum particle size of alkali hydroxide, and in particular NaOH or KOH, introduced is in the range of 10 to 100 ⁇ m, preferably in the range of 20 to 60 ⁇ m.
- the average maximum particle size corresponds to the arithmetic mean of the maximum sizes of several particles, preferably 20 particles.
- Another way is to use alkali hydroxide particles, and in particular NaOH or KOH, with at least 80% by number of said particles having a maximum size in the range of 10 to 100 ⁇ m, preferably in the range from 20 to 60 pm.
- the maximum size of a particle which, in general, is of irregular shape, corresponds to its largest dimension, in particular measured with a microscope, and preferably a visible light microscope. This last variant of determining the size of the particles used, which is not the preferred one, can be obtained on a population of 10, or preferentially, of 20 particles.
- the size of the particles introduced can be adjusted by different crushing or grinding techniques, for example by using an appropriate crushing device, such as an IKA® A11 grinder.
- bituminous compositions are preferably obtained from a bitumen base and NaOH, and/or KOH, CO2, and optionally one or more components defined in the scope of the invention.
- the alkaline hydroxide introduced represents from 0.1 to 8% by mass, preferably from 0.2 to 3% by mass, and preferably from 0.2 to 1.5% by mass, relative to the total mass of the bituminous composition.
- the alkali metal hydroxide introduced represents from 0.1 to 9% by mass, preferably from 0.2 to 4.5% by mass, and preferentially from 0.2 to 2% by mass, per relative to the mass of the bitumen base present in the bituminous composition.
- bituminous compositions according to the invention may also include an adhesion promoter, chosen in particular from amines, diamines, polyamines, alkyl amido amines, amidopolyamines, imidazolines, and their mixtures.
- adhesion promoters are in particular described in application WO 2018/206489 to which reference may be made for more details.
- adhesion promoter is chosen from:
- R is a saturated or unsaturated, substituted or unsubstituted, optionally branched or cyclic hydrocarbon group comprising 8 to 24 carbon atoms, for example, R is a hydrocarbon group derived from fatty acids of soot or fatty acids of tall oil;
- Ri and R 2 are a hydrogen atom or a hydrocarbon group comprising from 1 to 24 carbon atoms; Ri and R 2 are preferably hydrogen or methyl;
- - L represents a linear or branched hydrocarbon chain comprising from 1 to
- Amidopolyamines of formula (IV) and imidazolines wherein R and L are as defined for (I) and (II), and p is an integer greater than or equal to 1, in particular p is an integer in the range from 1 to 10.
- the adhesion promoter is selected from amines, diamines, polyamines, alkyl amido amines and amidopolyamines comprising a fatty chain, and in particular from those previously described.
- the adhesion promoter is an amidopolyamine comprising a fatty chain, of formula: Or:
- - p is an integer greater than or equal to 1, in particular p is an integer in the range from 1 to 10,
- R is a saturated or unsaturated, substituted or unsubstituted, optionally branched or cyclic hydrocarbon group comprising 8 to 24 carbon atoms.
- the adhesion promoter used in the bituminous compositions according to the invention is a mixture of amidopolyamines of formula (IV) in which p is an integer in the range from 1 to 10, L is - (CH 2 ) 2 -, and R corresponds to the hydrocarbon chains of the fatty acids of tall oil.
- said adhesion promoter when present, preferably represents 0.01 to 2% by mass, preferentially 0.05% to 1% by mass, and even more preferably 0, 1 to 0.3% by mass, of the total mass of the bituminous composition according to the invention.
- the adhesion promoter represents 0.01 to 2.5% by mass, preferably 0.05% to 1.1% by mass, and even more preferably 0.1 to 0.4 % by mass, relative to the mass of the bitumen base present in the bituminous composition.
- the bituminous compositions according to the invention may also include one or more polymers.
- an olefinic polymer and/or an elastomer, in particular a crosslinked or crosslinkable elastomer can be incorporated into the bituminous compositions according to the invention.
- bituminous compositions according to the invention may, in particular, comprise one or more olefinic polymers chosen in particular from: (a1) random or block copolymers, preferably random, of ethylene and of a monomer chosen from glycidyl acrylate and glycidyl methacrylate, comprising from 50% to 99.7% by mass, preferably from 60% to 95% by mass, more preferably 60% to 90% by mass of ethylene;
- (c1) the copolymers resulting from the grafting of a monomer B chosen from glycidyl acrylate and glycidyl methacrylate, onto a polymeric substrate;
- the polymeric substrate is chosen from polyethylenes, in particular low-density polyethylenes, polypropylenes, random or block copolymers, preferably random, of ethylene and vinyl acetate and random or block copolymers, preferably random, ethylene and C1 to C6 alkyl acrylate or C1 to C6 alkyl methacrylate, comprising from 40% to 99.7% by mass, preferably from 50% to 99% by mass of ethylene; preferably said graft copolymers comprising from 0.5% to 15% by mass, preferably from 2.5% to 15% by mass of graft units derived from monomer B.
- bituminous compositions according to the invention may, in particular, comprise one or more elastomers, in particular chosen from crosslinked or crosslinkable elastomers.
- Cross-linked elastomers will be introduced in their crosslinkable form in the compositions according to the invention and crosslinked in situ.
- Such elastomers known to be incorporated into a bituminous composition are, in particular, SB copolymers (block copolymer of styrene and butadiene), SBS (block copolymer of styrene-butadiene-styrene), SIS (styrene-isoprene-styrene), SBS* (styrene-butadiene-styrene star block copolymer), SBR (styrene-b-butadiene-rubber), EPDM (modified ethylene propylene diene).
- SB copolymers block copolymer of styrene and butadiene
- SBS block copolymer of styrene-butadiene-styrene
- SIS styrene-isoprene-styrene
- SBS* styrene-butadiene-styrene star block cop
- a bituminous composition according to the invention comprises from 0.05% to 10% by mass, preferably from 0.1% to 8% by mass and preferentially from 0.3 to 6% by mass, of olefinic polymer(s) and/or elastomer(s), relative to the total mass of said bituminous composition.
- the mass of olefinic polymer(s) and/or elastomer(s) represents from 0.1 to 12% by mass, preferably from 0.3 to 10%, and preferentially from 0.5 to 7% by mass, relative to the mass of the bitumen base present in the bituminous composition.
- Bituminous compositions also called bituminous compositions, according to the invention
- bituminous compositions according to the invention comprise one or more other additives, in particular chosen from those conventionally used in bituminous compositions, preferably the bitumen base, the CO 2 trapped , the alkali metal hydroxide, even the adhesion promoter and/or the elastomer and/or the olefinic polymer represent at least 90% by mass, preferably at least 95% by mass, even 100% by mass of the total mass of the bituminous composition.
- bituminous composition The various components of the bituminous composition are dispersed in the bituminous composition, and therefore in the bitumen base.
- bituminous compositions comprising a bitumen base modified by incorporating an alkali metal hydroxide and in which CO 2 has been incorporated and remains trapped, optionally under a form that has chemically reacted with another component present in the composition.
- bituminous compositions comprise a bitumen base, modified by incorporating:
- bitumen base preferably from 0.2 to 4.5% by mass, and preferably from 0.2 to 2% by mass relative to the mass of bitumen base, of alkaline hydroxide, and in particular NaOH or KOH or a mixture thereof,
- an adhesion promoter chosen from amines, diamines, polyamines, alkyl amido amines, amidopolyamines, imidazolines, and mixtures thereof, in an amount of 0.01 to 2.5% by mass, preferably from 0.05 to 1.1 % by mass, and even more preferably from 0.1 to 0.4% by mass, of the mass of the bitumen base,
- bituminous composition which remains trapped in said composition, optionally in a form having reacted chemically with another component present in said bituminous composition, and which represents from 0.5 to 5% by mass, preferably 0.5 to 4% by mass, and preferably from 0.5 to 3% by mass, and even more preferably from 0.5 to 2% or even from 0.5 to 1.5% or even from 0.7 to 2% by mass , relative to the mass of the bitumen base.
- compositions below are particularly preferred:
- bituminous compositions which comprise a bitumen base, modified by incorporating:
- bitumen base alkaline hydroxide, and in particular NaOH or KOH or one of their mixtures,
- an adhesion promoter chosen from amines, diamines, polyamines, alkyl amido amines, amidopolyamines, imidazolines, and mixtures thereof, at a rate of 0.01 to 2.5% by mass relative to the mass of the bitumen base,
- bituminous composition which remains trapped in said composition, optionally in a form which has reacted chemically with another component present in said bituminous composition, and which represents from 0.5 to 5% by mass, preferably 0.5 to 4% by mass, and preferably from 0.5 to 3% by mass, and even more preferably from 0.5 to 2% or even from 0.5 to 1.5% or even from 0.7 to 2% by mass, relative to the mass of the bitumen base;
- bituminous compositions which comprise a bitumen base, modified by incorporating:
- bitumen base from 0.2 to 4.5% by mass relative to the mass of bitumen base, alkaline hydroxide, and in particular NaOH or KOH or one of their mixtures,
- an adhesion promoter chosen from amines, diamines, polyamines, alkyl amido amines, amidopolyamines, imidazolines, and mixtures thereof, at a rate of 0.05 to 1.1% by mass, relative to the mass of the bitumen base ,
- bituminous composition which remains trapped in said composition, optionally in a form having reacted chemically with another component present in said bituminous composition, and which represents from 0.5 to 5% by mass, preferably 0.5 to 4% by mass, and preferably from 0.5 to 3% by mass, and even more preferably from 0.5 to 2% or even from 0.5 to 1.5% or even from 0.7 to 2% by mass per ratio to the mass of the bitumen base;
- bituminous compositions which comprise a bitumen base, modified by incorporating:
- bitumen base alkaline hydroxide, and in particular NaOH or KOH or one of their mixtures,
- an adhesion promoter chosen from amines, diamines, polyamines, alkyl amido amines, amidopolyamines, imidazolines, and mixtures thereof, at a rate of 0.1 to 0.4% by mass, relative to the mass of the bitumen base ,
- bituminous composition which remains trapped in said composition, optionally in a form having reacted chemically with another component present in said bituminous composition, and which represents from 0.5 to 5% by mass, preferably 0.5 to 4% by mass, and preferably from 0.5 to 3% by mass, and even more preferably from 0.5 to 2% or even from 0.5 to 1.5% or even from 0.7 to 2% by mass, relative to the mass of the bitumen base.
- adhesion promoter(s), or even the polymer(s) present are chosen from those specifically described in the context of the present description.
- the trapped CO2 reacts with the alkaline hydroxide introduced into the composition.
- the alkaline hydroxide is NaOH
- the alkaline hydroxide is KOH
- the alkaline hydroxide is KOH
- the latter may be found, within the bituminous composition, totally or partially in the form of one or more reaction products with the trapped CO2, in particular in the form of a mixture of KHCO3 and K2CO3, or even exclusively in the form of KHCO3.
- bitumen base represents at least 72% by mass of the total mass of the bituminous composition, and preferably at least 83%, even at least 89% and even at least 95% by mass of the total mass. of the bituminous composition. This % will depend on the presence or not of additional polymers, in particular.
- the bitumen base may be modified only by incorporating the components listed.
- these bituminous compositions will advantageously have a mass which remains stable at 25° C. and under 1013.25 hPa, over a period Ps of at least 10 hours, preferably of at least 15 hours. This stability criterion is as previously defined in the context of the present description.
- bituminous compositions of the invention can be prepared by any method known to those skilled in the art. Typically, these processes include mixing the components and heating the mixture.
- the bitumen can be heated before mixing. Usually, the bitumen is heated before mixing, and the additive or additives are added to the bitumen without having been heated beforehand.
- a bitumen composition is prepared by bringing into contact:
- bitumen base is used in an amount such that in the end it represents at least 72% by mass of said bituminous composition obtained.
- the mixture of the bitumen base and the alkali metal hydroxide, or even of the other additive(s) present is carried out at temperatures ranging from 90 to 230° C., preferably ranging from from 120 to 200°C, and preferably ranging from 120 to 180°C.
- Such a mixture is produced with stirring, in particular, for a period of 5 minutes to 10 hours, preferably 10 minutes to 3 hours, preferably 10 to 90 minutes, and even more preferably 20 to 90 minutes.
- Mixing can be carried out using high shear agitation or low shear agitation.
- the mixing is carried out with stirring at 100 to 1000 rpm (rotations per minute), preferably at 100 to 600 rpm, and preferably at 150 to 500 rpm.
- Agitation is carried out in such a way as to facilitate the dispersion and good distribution of the alkali hydroxide in the base bitumen.
- a person skilled in the art will adjust the stirring time and power to obtain a satisfactory distribution.
- an adhesion promoter and/or one or more polymers are incorporated into the bitumen base, they are preferably introduced after the alkali metal hydroxide.
- the incorporation of CO 2 within the composition leading to its trapping in the bitumen base is carried out, after the incorporation of the alkali metal hydroxide, and if one or more other components are incorporated, preferably after this incorporation also.
- Such trapping can be carried out by placing the bitumen base modified by incorporating alkali metal hydroxide, or even one or more additives, in a chamber under CO 2 pressure, the chamber being maintained at a temperature, generally ranging from 10 to 200°C, preferably ranging from 20 to 160°C, in particular from 25 to 160°C.
- the CO 2 pressure will in particular be chosen in the range going from 5.10 3 to 8.10 4 hPa (Hectopascal, corresponding to 5-80 bars), preferably in the range going from 5.10 3 to 5.10 4 hPa, and preferentially in the range going from 1.10 4 to 3.10 4 hPa. Maintenance under these conditions in the pressure vessel will be ensured for a period, most often from 5 minutes to 100 hours. This duration will be adapted, by those skilled in the art, depending in particular on the temperature chosen during the incorporation of the CO 2 , the pressure of CO 2 used and the quantity of CO 2 desired.
- the incorporation of CO 2 will be carried out over a period of 5h to 50h, when a temperature of 80 to 160°C is used, and over a period of 30 minutes to 5 hours when a temperature of 10 to 40 °C will be used, for the same pressure.
- the CO 2 incorporation step can be carried out with or without the presence of mechanical stirring. If such agitation is present, the agitation speed can, for example, vary between 200 rpm and 6000 rpm.
- the incorporation of CO 2 is favored at the lowest temperatures.
- Those skilled in the art will be able to play on the 3 variables T°C/Pressure and duration of exposure of the composition to a CO 2 pressure, to obtain optimal incorporation of CO 2 within the composition, and in particular to obtain saturation of the composition with CO 2 .
- the trapped C0 2 represents from 0.8 to 5.8% by mass, preferably from 0.8 to 4.5% by mass, preferably from 0.8 to 3.5% by mass, and even more preferably from 0.8 to 2.6% by mass, or even from 0.8 to 1.8% by mass, of the mass of the bitumen base.
- This release step or phase Pr is generally at least 3 hours, or even at least 5 hours, most often 5 to 10 hours, and typically 5 hours, after the end of the trapping step of the CO2 .
- the end of the CO 2 trapping step corresponds, in particular, to the moment when the bituminous composition is no longer under a CO 2 pressure. This release can occur naturally when the bituminous composition is stored at 25° C. and under 1013.25 hPa.
- Such a release phase under these conditions typically lasts at least 5 hours, and in particular from 5 to 10 hours.
- bituminous composition it is also possible for the bituminous composition to be subjected to heating during this Pr release phase, which will have the effect of accelerating the release of part of the CO 2 and therefore of reducing the duration of the release phase.
- a quantity corresponding to a quantity of 0.1 to 0.7% by mass of CO 2 relative to the bitumen mass can be salted out, and results in a mass % of CO 2 relative to the mass of the bitumen base, which still remains at least equal to 0.5%, and typically in the range of 0.5 to 5%, from 0.5 to 4%, from 0.5 to 3%, from 0.5 to 2% or from 0.5 to 1.5% or from 0.7 to 2%.
- the remaining CO 2 remains trapped within the bituminous composition, under so-called standard storage conditions (at 25°C and under 1013.25 hPa), which results in stabilization of the mass of the bituminous composition.
- the mass of the bituminous composition is understood as the mass of all the components present (in particular the bitumen base, the alkaline hydroxide introduced, and the other components possibly present) but also of the CO 2 trapped in the bituminous composition when the mass of it is measured.
- the so-called trapped CO 2 can therefore be in the form of CO 2 and reaction product(s) with the alkaline hydroxide, such as NaHCO 3 and Na 2 CO 3 when the alkaline hydroxide is NaOH or such as KHCO 3 and K 2 CO 3 when the alkaline hydroxide is KOH.
- the CO 2 which is eliminated during this Pr release phase can be all or part of the CO 2 trapped in the composition, still in the CO 2 form.
- the invention also relates to the bituminous compositions capable of being obtained by the process described in the context of the invention, and in particular the bituminous compositions, which can be qualified as stabilized, which are capable of being obtained at the end of the step of releasing part of the trapped CO 2 .
- bituminous compositions obtained according to the invention can be used as bituminous binder.
- the bituminous binder or bituminous composition according to the invention can in turn be used to prepare a combination with aggregates, in particular road aggregates.
- the invention relates in particular to bituminous coated materials as materials for the construction and maintenance of pavement bodies and their surfacing, as well as for carrying out all road works.
- bituminous mix a mixture of a bituminous binder with aggregates and optionally mineral and/or synthetic fillers.
- the bituminous mix comprises a bituminous binder as described in the context of the invention, and optionally mineral and/or synthetic fillers, preferably chosen from fines, sand, gravel and recycled millings.
- Aggregates are mineral and/or synthetic aggregates, in particular, recycled millings, with dimensions greater than 2 mm, preferably between 2 mm and 20 mm.
- the invention also relates to a process for preparing a bituminous mix comprising the hot mixing of a bituminous composition according to the invention, with aggregates, and optionally mineral and/or synthetic fillers.
- bituminous binder according to the invention can advantageously be used to prepare a surface dressing, a hot mix, a cold mix, a cold mix or a serious emulsion.
- the invention also relates to asphalts as materials for manufacturing and covering sidewalks.
- asphalt is meant a mixture of bituminous binder with mineral and/or synthetic fillers.
- An asphalt comprises a bituminous composition as described in the context of the invention and mineral fillers such as fines, sand or gravel and/or synthetic fillers.
- the mineral fillers consist of fines (particles with dimensions less than 0.063 mm), sand (particles with dimensions between 0.063 mm and 2 mm) and optionally gravel (particles with dimensions greater than 2 mm, preferably between 2 mm and 4mm).
- Asphalt has 100% compactness and is mainly used to make and cover sidewalks, while asphalt has less than 100% compactness and is used to make roads. Unlike asphalt mixes, asphalts are not compacted with a roller during their placement.
- the invention also relates to a process for preparing an asphalt comprising the hot mixing of a bituminous composition according to the invention, with mineral and/or synthetic fillers.
- bitumen composition in various industrial applications, in particular for preparing a sealing coating, a membrane or an impregnation layer.
- industrial applications of bituminous compositions mention may be made of the manufacture of waterproofing membranes, noise-reducing membranes, insulation membranes, surface coatings, carpet tiles, impregnation layers.
- the compositions according to the invention Due to the incorporation of CO2, the compositions according to the invention have a lower viscosity than conventional bituminous compositions. It is thus possible to implement them using lower temperatures.
- the invention also relates to processes for preparing an asphalt mix comprising the hot mixing, at a temperature of 80 to 200° C., preferably of 80 to 180° C. and preferentially of 100 to 160° C., of a bituminous composition according to the invention or capable of being obtained according to a process according to the invention, with aggregates and/or recycling millings, and optionally mineral and/or synthetic fillers.
- the invention also relates to a process for preparing an asphalt comprising hot mixing, at a temperature of 80 to 200° C., preferably of 80 to 180° C. and preferably of 100 to 160° C. , of a bituminous composition according to the invention or capable of being obtained according to a process according to the invention, with mineral and/or synthetic fillers.
- the invention also relates to the use of an alkaline hydroxide in a bituminous composition in which CO 2 is incorporated, to obtain stabilization of the quantity of CO 2 remaining trapped within said bituminous composition.
- bituminous composition and/or the process for preparing a composition according to the invention apply to the uses, products and processes described in this section. Also, to obtain stabilization of the quantity of CO 2 remaining trapped within said bituminous composition, the components and quantities as previously defined, and/or the incorporation and/or storage conditions will advantageously be applied.
- Figure 1 represents the evolution of the % of CO 2 remaining in the sample (% by mass relative to the mass of the total composition at time t) as a function of the time elapsed after leaving the PAV (h), for compositions F3-1, F3-2, F3-3 and pure bitumen.
- FIG. 2 represents the change in the mass of the bituminous compositions (g) as a function of the time elapsed after leaving the PAV (h), for the compositions F3-1, F3-2, F3-3 and pure bitumen.
- FIG. 3 represents the evolution of the phase angle (°) as a function of the complex shear modulus (Pa), for the compositions F3-1 after incorporation of CO2 and F3-1 as such.
- Figure 4 represents the evolution of the Phase Angle (°) as a function of the Complex Shear Modulus (Pa), for the compositions F3-1 after incorporation of CO2 and F3-1 after aging for 25 hours ( v25h).
- Figure 5 represents the evolution of the remaining CO2 (% by mass relative to the bitumen base mass) as a function of the time elapsed after leaving the PAV (h), for the compositions pure bitumen, F3-1, Dellite, Sepiolite, F3-2, F3-3 and F8, after CO2 incorporation.
- Figure 6 shows the solid sodium NMR spectra of a bituminous composition according to the invention at a given time tO, then at tO+8 months of storage at room temperature (25°C), as well as the reference spectrum NaHCO 3 .
- the adhesion promoter H1 was an amino additive: WETFIX BE from Akzo Nobel Surface Chemistry AB (CAS 68910-93-0).
- the soda sodium hydroxide
- the soda sodium hydroxide was supplied in the form of anhydrous pellets (CARL ROTH GMBH & Co. KG, Article No. 9356.1) and its purity was greater than 99%.
- the sodium hydroxide pellets were ground into a fine powder, using an IKA® A11 grinder (IKA-Werke GmbH & Co) at 28,000 rpm, for approximately 30 seconds, resulting in hydroxide particles of sodium (NaOH). Their average maximum size measured on 20 particles using a microscope was about 50 ⁇ m.
- the adhesion promoter was then introduced at 0.2% by mass, relative to the bitumen + NaOH + adhesion promoter mass.
- a PAV device model of the device used: PAV3 from the company ATS [Applied Test Systems] was used.
- This device is usually used to induce oxidation of bitumen, according to standard NF EN 14769. It simulates the long-term oxidative aging of a bitumen composition, representing an oxidation of several years on the road. This test is usually carried out at a temperature of 100°C, at a pressure of 21 bar and for 20 hours using a bottle of compressed air.
- the bitumen is introduced into the device in cups each containing 50 g of bitumen composition.
- the % NaOH and % CO 2 are % by mass of the quantity incorporated, given with respect to the mass of the bitumen base used.
- the % CO 2 is obtained by weighing the samples, before and after the trapping step under PAV, then over time.
- the relative % of CO 2 is the % of CO 2 still incorporated at a given time, compared to the % of CO 2 incorporated at the PAV outlet.
- % variation tO for the mass of the composition is the % variation obtained by comparing the mass of the composition at a given instant and that at the output of the PAV.
- % variation 5 h for the mass of the composition is the % variation obtained by comparing the mass of the composition at a given instant and that obtained after 5 h at 25° C. after leaving the PAV.
- compositions presented in Table 1 were prepared with incorporation of the adhesion promoter, at a level of 0.2% by mass, relative to the mass bitumen + NaOH + adhesion promoter, which also corresponds at 0.2% by mass relative to the mass of bitumen alone.
- PAV and the % of CO 2 are given in % by mass relative to the mass of the bitumen base (more simply called pure bitumen in the table) or in relation to the total mass of the bituminous composition (at the time indicated) therefore including bitumen+NaOH+WETIX BE+CO2 (more simply called composition or compound in the table).
- bitumen+NaOH+WETIX BE+CO2 more simply called composition or compound in the table.
- the relative % CO 2 is the % of CO 2 remaining with respect to the % of CO 2 incorporated at the outlet of the PAV.
- Figure 1 and Figure 2 clearly show stabilization of the mass of the bituminous compositions according to the invention, after a short period of release of CO2 (at most during the first 5 hours following the end of the PAV cycle set implemented for the capture of CO2). In the absence of soda, the release of CO 2 continues over a much longer period.
- the bitumen base not modified by the addition of sodium hydroxide contains only a quantity of CO2 which represents 0.36% of the mass of CO2 initially incorporated (% relative), whereas in the case of the compositions according to the invention, the latter is always greater than 0.5%.
- a weighing was also carried out after a storage period of 168 hours at 25° C.
- the release of the CO2 is materialized by a change in appearance of the bituminous composition, the surface of which has asperities and reliefs due to the degassing of the CO 2 .
- bitumen can be handled and stored hot, around 160°C. Consequently, hot desorption was also investigated, for composition F 3-1 .
- composition F 3-1 hot desorption was also investigated, for composition F 3-1 .
- a sample of it was placed in a microchamber, for 1 hour at 160°C. The amount of CO2 released during the experiment was measured and only corresponded to about 10% of the mass of CO 2 trapped, before this heating phase.
- FIG. 6 represents the solid sodium NMR spectra of composition F 3-3 according to the invention at a given instant tO located after the release phase for 24 hours, then at tO+8 months of storage at room temperature (25° C), as well as the NaHCO 3 reference spectrum.
- the spectra are obtained by Nuclear Magnetic Resonance of the 23 Na nucleus on a 300 MHz spectrometer, on solid samples rotated at the magic angle at a frequency of 8 kHz, by direct pulse with heteronuclear decoupling of the 1 H nuclei. 256 scans were acquired for each spectrum.
- bituminous compositions were evaluated when their mass had stabilized at 25°C. The following assessments were carried out by:
- the % NaOH and % CO 2 are % by mass of the quantity incorporated, given with respect to the mass of the bitumen base used.
- the % CO 2 is obtained by weighing the samples, before and after the trapping step under PAV, then over time.
- the relative % of CO 2 is the % of CO 2 still incorporated at a given time, compared to the % of CO 2 incorporated at the PAV outlet.
- % variation tO for the mass of the composition is the % variation obtained by comparing the mass of the composition at a given instant and that at the output of the PAV.
- % variation 5 h for the mass of the composition is the % variation obtained by comparing the mass of the composition at a given instant and that obtained after 5 h at 25° C. after leaving the PAV.
- compositions presented in Table 3 were prepared with incorporation of the adhesion promoter, at a level of 0.2% by mass, relative to the bitumen mass.
- bituminous compositions for which the incorporation of CO2 is carried out at 25° C. have a greater quantity of CO2 incorporated, and that, moreover, the incorporation is more stable over time. It also appears that the incorporation of CO2 increases with the quantity of sodium hydroxide incorporated into the bituminous composition.
- the amount of additive was 3.0% m/m relative to the total mass of the bituminous composition obtained, corresponding to 3.1% m/m relative to the mass of the bitumen base.
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Abstract
Description
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CA3233820A CA3233820A1 (fr) | 2021-10-08 | 2022-10-06 | Compositions bitumineuses modifiees par incorporation d'hydroxyde alcalin et piegeant du co2, procedes et utilisations associes |
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FRFR2110676 | 2021-10-08 | ||
FR2110676A FR3127949A1 (fr) | 2021-10-08 | 2021-10-08 | Compositions bitumineuses modifiées par incorporation d’hydroxyde alcalin et piégeant du CO2, procédés et utilisations associés |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB246907A (en) * | 1924-11-03 | 1926-02-03 | Asphalt Cold Mix Ltd | Improvements in or relating to bituminous emulsions |
WO2010051458A1 (fr) * | 2008-10-31 | 2010-05-06 | Calera Corporation | Compositions non cimentaires comprenant des additifs séquestrant le co2 |
WO2018206489A1 (fr) | 2017-05-09 | 2018-11-15 | Total Marketing Services | Compositions bitumineuses comprenant un additif aminé et un hydroxyde, leur procédé de préparation et leurs applications |
WO2019122670A1 (fr) | 2017-12-19 | 2019-06-27 | Total Marketing Services | Compositions bitumineuses comprenant une argile a temperature de degradation elevee |
-
2021
- 2021-10-08 FR FR2110676A patent/FR3127949A1/fr active Pending
-
2022
- 2022-10-06 CA CA3233820A patent/CA3233820A1/fr active Pending
- 2022-10-06 WO PCT/FR2022/051884 patent/WO2023057723A1/fr active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB246907A (en) * | 1924-11-03 | 1926-02-03 | Asphalt Cold Mix Ltd | Improvements in or relating to bituminous emulsions |
WO2010051458A1 (fr) * | 2008-10-31 | 2010-05-06 | Calera Corporation | Compositions non cimentaires comprenant des additifs séquestrant le co2 |
WO2018206489A1 (fr) | 2017-05-09 | 2018-11-15 | Total Marketing Services | Compositions bitumineuses comprenant un additif aminé et un hydroxyde, leur procédé de préparation et leurs applications |
WO2019122670A1 (fr) | 2017-12-19 | 2019-06-27 | Total Marketing Services | Compositions bitumineuses comprenant une argile a temperature de degradation elevee |
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CA3233820A1 (fr) | 2023-04-13 |
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