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    • 专利摘要:
    An aqueous composition comprising an NOx reducing agent or a precursor of such an agent, especially urea, and at least one paraffin dispersed in the aqueous phase. Such a composition makes it possible to reduce the formation of deposits in an exhaust line SCR while avoiding foaming during its handling.
    公开号:FR3044564A1
    申请号:FR1561762
    申请日:2015-12-02
    公开日:2017-06-09
    发明作者:Annabelle Collin
    申请人:Total Marketing Services SA；
    IPC主号:
    专利说明:

    UREA-BASED COMPOSITION FOR THE TREATMENT OF GASES
    EXHAUST
    The present invention relates to a composition for the treatment of exhaust gases at the outlet of onboard or stationary diesel engines. It also relates to its use in any device for treating these exhaust gases, whether the engines are heavy-duty engines or engines for light vehicles or engines for stationary industrial applications.
    State of the art
    European pollution standards for diesel fuels, in particular for heavy-duty vehicles, have led engine manufacturers to implement exhaust aftertreatments. These post-treatments include SCR (Selective Catalytic Reducer), EGR (Exhaust Gas Recirculation) and FAP (particulate filter) technologies. These various aftertreatments can be installed alone or in combination in that they do not always act on the same pollutants present in the exhaust gas.
    To meet the standard, in particular the Euro 6 standard, which applies in Europe to all vehicles from 1 September 2015, most European motor vehicle manufacturers have opted for SCR aftertreatment at exhaust of their engines, this post-treatment acting exclusively on the reduction of nitrogen oxides present in the gases. Another advantage of this technique is that it allows, through optimized engine settings, a significant reduction in fuel consumption.
    The SCR after-treatment consists in reducing the NOx or nitrogen oxides (NO, NO 2) on a catalyst containing platinum and palladium, and in the presence of a reducing agent, generally ammonia gas. To introduce gaseous ammonia into the exhaust, it is known to produce it directly in the pipe before the SCR system by vaporizing an aqueous solution of urea. Urea being injected at an average temperature generally ranging from 150 to 400 ° C, gradually hydrolyzes to gaseous ammonia. Optionally, other ammonia precursor agents may be employed under similar conditions.
    In some configurations of SCR and ammonia precursor injection, in particular urea injection, the builders have noted the appearance of deposits in the exhaust pipes before the entry of the SCR . These deposits may be large enough to cause partial or complete closure of the exhaust duct related to the exhaust pressure against and thus create engine power losses. In a constant injection configuration, the amount of deposits formed is greater at low temperatures than at high temperatures. These deposits, according to the analyzes that have been made, consist mainly of cyanuric acid resulting from the incomplete decomposition of urea. This cyanuric acid can sublime and produce ammonia gas again. However, this reaction can occur at very high temperature, higher than 450 ° C, temperature rarely reached at this point in the exhaust pipes.
    It has been found in particular that these deposits were present in the pipes with bends due to the lack of space in the vehicle, and when the distance between the urea injection and the first bend is too short. The hypothesis formulated is that in this type of configuration, some of the drops of urea do not have time to vaporize and completely decompose into gaseous ammonia. The drops of urea are deposited on the wall of the conduit which is at a temperature too low to allow complete decomposition into ammonia gas, and they only partially decompose forming cyanuric acid deposits stuck to the wall. Furthermore, it was also found that depending on the configuration of the SCR line, the urea was likely to crystallize in the line, resulting in an obstruction of the line. WO2008 / 125745 discloses an aqueous solution comprising a major portion of a constituent capable of releasing ammonia gas above 200 ° C and a minor portion of at least one polyfunctional additive whose HLB varies from 7 to 17 to limit the formation of cyanuric acid deposits in any spraying device for the aftertreatment of exhaust gases, more particularly SCR devices. The polyfunctional additives used include polyalkoxylated fatty alcohol ethers and polyalkoxylated fatty alcohol esters. EP2337625 describes a mixture of surfactants making it possible to reduce the droplet diameter of an aqueous urea solution, and thus promote its vaporization and the transformation of urea into gaseous ammonia in an SCR system. The proposed solution consists of a mixture of polyalkoxylated fatty alcohols, with controlled degrees of alkoxylation. EP2488283 discloses urea solution additives of the particular polyalkoxylated fatty alcohol type. These additives are also intended to promote a reduction in the formation of deposits from the decomposition of urea in SCR systems.
    However, it has been found that certain solutions of ammonia precursor, in particular urea, additive, when introduced into the tank, have a tendency to foam. This foaming hinders the filling of the tank and can cause it to overflow. In addition, this foaming can cause the injection of air into the system. This phenomenon disrupts the control of the amount of solution injected.
    One solution to this problem is to add anti-foam agents. But such additives represent a significant additional cost.
    There remains therefore the need for an additive for aqueous solutions based on an NOx reducing agent, for example ammonia or a precursor of said reducing agent, such as urea, making it possible to form a composition with properties optimized for use on an SCR line. This composition is expected to be able to avoid or reduce deposits when used on an SCR line. It is also expected from this composition that it has reduced foaming compared to additive compositions based on an NOx reducing agent or a precursor of said reducing agent, such as urea of the prior art. This composition is also expected to allow a precise dosage of the amounts of composition injected. Summary of the Invention The invention relates to an aqueous composition comprising an NOx reducing agent or a precursor of a NOx reducing agent, in particular urea, characterized in that it comprises at least one paraffin dispersed in the aqueous phase. The invention relates in particular to an aqueous composition comprising at least one NOx reducing agent or a precursor of a NOx reducing agent, characterized in that it comprises at least one paraffin dispersed in the aqueous phase, said paraffin representing 50 at 10,000 ppm by mass with respect to the NOx reducing agent mass or with respect to the NOx reducing agent precursor mass.
    According to a preferred embodiment, the precursor of the NOx reducing agent is urea.
    According to a preferred embodiment, the C20-C36 paraffins represent at least 90% by weight relative to the total mass of paraffins in the composition.
    According to a preferred embodiment, the composition comprises at least one surfactant, and optionally an emulsion stabilizing agent.
    According to a preferred embodiment, the composition comprises at least one nonionic surfactant.
    According to a preferred embodiment, the composition comprises at least one nonionic surfactant chosen from oxygenated C4-C20 hydrocarbon molecules comprising one or two furanose or pyranose rings, and one or more hydroxyl groups, at least one of the hydroxyl groups being substituted. by a mono- or polyalkoxylated group.
    According to a still preferred embodiment, the nonionic surfactant is chosen from polyethoxylated sorbitans and polyethoxylated isosorbides.
    According to a preferred embodiment, the C4-C20 oxygenated hydrocarbon surfactants comprising one or two furanose or pyranose rings, and one or more hydroxyl groups, mono or polyalkoxylated, are present in amounts ranging from 1 to 70% by weight relative to to the total mass of paraffins in the composition.
    According to a preferred embodiment, the composition further comprises at least one emulsion stabilizing agent chosen from fatty acids.
    According to a preferred embodiment, the fatty acid is present in amounts ranging from 1 to 50% by mass relative to the total mass of paraffins in the composition.
    According to another preferred embodiment, the composition comprises at least one nonionic surfactant chosen from esters of fatty acids and oxygenated C4-C20 hydrocarbon molecules comprising one or two furanose or pyranose rings, and one or more hydroxyl groups, at least one of the hydroxyl groups being substituted by a mono- or polyalkoxylated group.
    According to a still more preferred embodiment, the nonionic surfactant (s) are chosen from mono- or poly-ethoxylated fatty acid and sorbitan esters and mono- or poly-ethoxylated fatty acid and isosorbide esters. .
    According to a preferred embodiment, the esters of fatty acids and oxygenated C4-C20 hydrocarbon molecules comprising one or two furanose or pyranose rings, and one or more hydroxyl groups, mono or polyalkoxylated, are present in amounts ranging from 1 to 70% by weight relative to the total mass of paraffins in the composition.
    According to a preferred embodiment, the composition comprises at least: a nonionic surfactant chosen from oxygenated C4-C20 hydrocarbon molecules comprising one or two furanose or pyranose rings, and one or more hydroxyl groups, at least one of the groups hydroxyls being substituted with a mono- or polyalkoxylated group, an emulsion stabilizer chosen in particular from C 8 -C 30 fatty acids, and a nonionic surfactant chosen from esters of fatty acids and of oxygenated hydrocarbon molecules. C4-C20 comprising one or two rings furanose or pyranose, and one or more hydroxyl groups, at least one of the hydroxyl groups being substituted by a mono- or poly-alkoxylated group.
    According to a preferred embodiment, the composition comprises at least: a nonionic surfactant chosen from oxygenated C4-C20 hydrocarbon molecules comprising one or two furanose or pyranose rings, and one or more hydroxyl groups, at least one of the groups hydroxyls being substituted with a mono- or polyalkoxylated group, an emulsion stabilizer chosen in particular from C 8 -C 30 fatty acids, and a nonionic surfactant chosen from esters of fatty acids and of oxygenated hydrocarbon molecules. C4-C20 comprising one or two furanose or pyranose rings, and one or more hydroxyl groups.
    According to a preferred embodiment, the set of surfactants and emulsion stabilizers represents from 1 to 100% by mass relative to the total mass of paraffin (s) in the composition. The invention also relates to the use of a composition as defined above, for the aftertreatment of the exhaust gas by Selective Catalytic Reduction catalyst (also referred to as SCR catalyst for Selective Catalytic Reducer).
    According to a preferred embodiment, the composition is used to prevent, limit, prevent the formation of deposits in an exhaust line SCR. The invention also relates to the use of a composition as defined above, to prevent or reduce foaming during filling of a reservoir by the composition. The invention also relates to a method for treating exhaust gases in an internal combustion engine, preferably a diesel engine equipped with an SCR system, this method being characterized in that it comprises at least one introduction step of a composition as defined above in the SCR line, upstream of the SCR system. The invention also relates to a method for reducing deposits in an SCR line, this method being characterized in that it comprises at least one step of introducing a composition as defined above into the SCR line, upstream of the SCR system.
    According to a preferred embodiment, the process comprises a step of preparing an aqueous composition of an NOx reducing agent, or a precursor of a NOx reducing agent, and of paraffin (s) as defined herein. -above. The invention also relates to the use of an emulsion or an aqueous dispersion or suspension of paraffin as an additive in an aqueous solution of a NOx reducing agent or a precursor of a NOx reducing agent. , for implementation in an SCR system.
    The compositions of the invention have many advantages: they can be used in the same way and in the same equipment as the solutions of the prior art. They are at least as effective, or even more effective, than the prior art solutions, including urea-based solutions in reducing or preventing deposit formation in SCR systems. They do not cause little or no foaming during handling and thus prevent overflowing during filling of the tank. They are storage stable. They allow precise control of the amount of composition injected.
    DETAILED DESCRIPTION The invention is based on the development of aqueous compositions comprising an NOx reducing agent or a precursor of a NOx reducing agent, in particular urea, and further comprising one or more paraffins dispersed in said composition. . This dispersion is advantageously stabilized by means of one or more surfactants, preferably nonionic surfactants.
    In the present application, the terms "dispersion" or "dispersed", used to designate aqueous compositions comprising paraffin also include emulsions, suspensions, and more generally any form of composition in which paraffin and water form a mixture substantially homogeneous. The NOx reducing agent or the precursor of said agent:
    The composition is prepared from an aqueous solution comprising at least one NOx reducing agent or at least one precursor of said agent.
    By "NOx reducing agent" is meant a compound capable of reducing at least partially, if not totally, NOx to gaseous ammonia, under the operating conditions of an SCR line, ie at a temperature ranging from 150 to 400 ° C. Among the reducing agents of NOx, mention may be made of ammonia.
    By "precursor of a NOx reducing agent" is meant a compound capable of releasing the NOx reducing agent under the effect of temperature and / or by catalytic reaction. Among the ammonia precursors, there may be mentioned urea which by hydrolysis reaction produces ammonia (NOx reducing agent) according to a well-known method. An exhaust line SCR may comprise, upstream of the catalytic system SCR, a catalyst whose function is to transform a precursor of a NOx reducing agent into an NOx reducing agent, in particular gaseous ammonia.
    Advantageously, the composition is prepared from an aqueous solution of urea. Indeed, urea has the advantage of being stable, non-volatile, non-explosive and non-flammable. It can be transported safely, stored and handled by an operator without specific training.
    Usually, the solution implemented in the SCR lines comprises 32.5% by weight of urea, so as to meet the ISO 22241-1 standard for reducing NOx in diesel engines.
    For this use, it is therefore expected that the composition has a concentration of urea substantially equal to 32.5% by mass. However, it is also within the scope of the present invention to prepare aqueous urea compositions of greater than 32.5% concentration which are diluted prior to processing. This variant makes it possible to save money during the transport of these urea-based compositions.
    Paraffins:
    The composition further comprises at least one paraffin.
    The paraffins are alkanes, whose crude formula is CnH2n + 2, with n being an integer ranging from 8 to 40. They include normal paraffins (linear) and isoparaffins (branched). They can be liquid, pasty or solid. Preferably, C20-C36 paraffins are selected. Advantageously, the C20-C36 paraffins represent at least 90% by weight of all the paraffins of the composition. Even better, the C22-C32 paraffins represent at least 90% by weight of all the paraffins of the composition.
    Preferably, the C20-C36 paraffins represent at least 95% by weight of all the paraffins of the composition. Even better, the C22-C32 paraffins represent at least 95% by weight of all the paraffins of the composition.
    The paraffins are introduced into the aqueous composition in quantities ranging from 50 to 10,000 ppm by weight of paraffins relative to the amount of urea by mass, preferably from 150 to 5000 ppm, more preferably from 300 to 3000 ppm, more advantageously from 300 to 1500 ppm.
    For an aqueous solution of urea with a concentration of 32.5% by weight of urea, the paraffins are introduced into the aqueous composition in quantities ranging from 15 to 3300 ppm by weight of paraffins relative to the mass of aqueous solution, preferably 50% by weight. at 1500 ppm, more preferably 100 to 1000 ppm, still more preferably 100 to 500 ppm.
    The surfactant system:
    The aqueous composition advantageously comprises at least one surfactant system which makes it possible to maintain the paraffin in dispersed form. The surfactant system makes it possible to form a paraffin emulsion in water.
    Preferably, the surfactant system comprises at least one nonionic surfactant. - First variant:
    According to a first variant, the nonionic surfactant or surfactants are chosen from oxygenated C4-C20 hydrocarbon molecules comprising one or two furanose or pyranose rings, and one or more hydroxyl groups, at least one of the hydroxyl groups being substituted by a grouping. mono- or polyalkoxylated.
    Oxygenated hydrocarbon molecule means a chain consisting exclusively of carbon, hydrogen and oxygen atoms, said chain being linear or branched, cyclic, polycyclic or acyclic, saturated or unsaturated, and optionally aromatic or polyaromatic. An oxygenated hydrocarbon chain may comprise a linear or branched part and a cyclic part. It may comprise an aliphatic part and an aromatic part.
    According to the invention, the oxygenated hydrocarbon molecules are advantageously saturated.
    According to the invention, the oxygenated hydrocarbon molecules advantageously comprise a linear part and a cyclic part.
    The cyclic portion may be monocyclic or polycyclic.
    According to the invention, the carbons of the mono- or polyalkoxylated groups are not counted in the oxygenated C4-C20 hydrocarbon molecule.
    Advantageously, the nonionic surfactants are chosen from oxygenated C4-C10 hydrocarbon molecules comprising one or two furanose or pyranose rings, and one or more hydroxyl groups, at least one of the hydroxyl groups being substituted with a mono- or poly- alkoxylated.
    Preferably, the surfactants used have an average degree of alkoxylation ranging from 1 to 80, more preferably from 1 to 50, more preferably from 5 to 25 and advantageously from 10 to 20. Generally, the mono- or polyalkoxylated groups are formed by the reaction of alkylene oxide condensation on the cyclic molecule carrying hydroxyl functions. It may be ethylene oxide groups, propylene oxide or mixtures of these monomers which form copolymers of ethylene oxide and propylene oxide, optionally block polymers.
    The grafting of alkoxylated groups on the hydroxyl functions can be done by condensation reaction on a hydroxyl function or on several hydroxyl functions of the molecule, depending on the number of hydroxyl groups present, their reactivity, and the reaction conditions. In general, the degree of average alkoxylation is defined as the number of moles of alkylene oxide which has been reacted with the molecule to be grafted.
    The surfactant system may also comprise polyalkylene oxide polymers and copolymers, in particular ethylene polyoxides, propylene polyoxides, copolymers of ethylene oxide and propylene oxide, optionally block polymers, or mixtures of these polymers. These polymers are sometimes formed in parallel with the grafting of the alkylene oxides on the hydroxyl functions of the C4-C20 oxygenated hydrocarbon molecule and remain in a mixture with these. Commercial products of the C4-C20 oxygenated hydrocarbon molecule type carrying hydroxyl functions grafted with alkylene oxides generally comprise minor amounts of these polyalkylene oxide polymers and copolymers.
    Preferably, the nonionic surfactant or surfactants are chosen from mono- or polyalkoxylated sorbitans and mono- or polyalkoxylated isosorbides and mixtures thereof. Even more preferably, the nonionic surfactant or surfactants are chosen from mono- or poly-ethoxylated sorbitans and mono- or poly-ethoxylated isosorbides, as well as their mixtures. These can be represented by the following formulas (I) and (II): ethoxylated sorbitans:
    (I)
    With m, n, p and q, identical or different, integers ranging from 0 to 20, the sum m + n + p + q ranging from 1 to 80, preferably from 1 to 50. - Ethoxylated isosorbides:
    (Π)
    With m, n, identical or different, integers ranging from 0 to 20, the sum m + n ranging from 1 to 40.
    Preferably, the mono- or poly-ethoxylated sorbitans and the mono- or poly-ethoxylated isosorbides used have an average degree of alkoxylation ranging from 1 to 50, advantageously from 5 to 25 and even more preferentially from 10 to 20.
    The alkoxylated C4-C20 oxygenated hydrocarbon molecules, in particular the mono- or poly-ethoxylated sorbitans and the mono- or poly-ethoxylated isosorbides, as well as their mixtures, are advantageously introduced into the aqueous composition in quantities ranging from 1 to 70%. mass in relation to the total mass of
    paraffins in the composition, preferably 1 to 50%, preferably 5 to 40%, more preferably 10 to 30%.
    According to this variant, the composition also advantageously comprises at least one or more emulsion stabilizers. In a known manner, these emulsion stabilizers may be chosen in particular from saturated or unsaturated C8-C30 fatty acids and mixtures thereof.
    The fatty acid or acids may be saturated or unsaturated and may be linear or branched, and their carbon number may be from 8 to 30, preferably from 10 to 24. The fatty acid may for example be a saturated fatty acid such as n-caproic acid, caprylic acid, n-capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid or unsaturated fatty acid such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid or docosahexaenoic acid. Stearic acid, myristic acid and palmitic acid are examples of preferred fatty acids. Preferably, the emulsion stabilizer is chosen from mixtures of C 10 -C 24 fatty acids, even more preferentially C 12 -C 24. C20.
    Advantageously, the invention uses a mixture of fatty acids including stearic acid, myristic acid and palmitic acid. Preferably, the invention uses a mixture of fatty acids consisting essentially of stearic acid, myristic acid and palmitic acid.
    The emulsion stabilizers are advantageously introduced into the aqueous composition in amounts ranging from 1 to 50% by mass relative to the total weight of paraffins in the composition, preferably from 5 to 40%, more preferably from 10 to 30%.
    According to this first variant, preferably, the surfactant system consists essentially of: one or more C4-C20 oxygenated hydrocarbon molecules comprising one or two furanose or pyranose rings, and one or more hydroxyl groups, at least one of the hydroxyl groups being substituted by a mono- or polyalkoxylated group, - one or more emulsion stabilizers chosen from C 8 -C 30 fatty acids and mixtures thereof.
    Even more preferentially, according to this variant, the surfactant system consists essentially of: one or more molecules chosen from mono- or poly-ethoxylated sorbitans and mono- or poly-ethoxylated isosorbides, one or more emulsion stabilizers chosen from C10-C24 fatty acids and mixtures thereof.
    Advantageously, according to this variant, the surfactant system consists essentially of: one or more molecules chosen from the mono- or poly-ethoxylated sorbitans of formula (I) and the mono- or poly-ethoxylated isosorbides of formula (II), as defined above, - one or more emulsion stabilizers selected from C12-C20 fatty acids and mixtures thereof. - Second variant:
    According to a second variant, the nonionic surfactant or surfactants are chosen from esters of fatty acids and oxygenated C4-C20 hydrocarbon molecules comprising one or two furanose or pyranose rings, and one or more hydroxyl groups, at least one of hydroxyl groups being substituted by a mono- or polyalkoxylated group. The fatty acid may be grafted onto a hydroxyl group of the ring or at the end of an alkoxylated chain.
    According to the invention, the oxygenated hydrocarbon molecules are advantageously saturated.
    According to the invention, the oxygenated hydrocarbon molecules advantageously comprise a linear part and a cyclic part.
    The cyclic portion may be monocyclic or polycyclic.
    According to the invention, the carbons of the mono- or polyalkoxylated groups are not counted in the oxygenated C4-C20 hydrocarbon molecule.
    Advantageously, the nonionic surfactants are chosen from esters of fatty acids and oxygenated C4-C10 hydrocarbon molecules comprising one or two furanose or pyranose rings, and one or more hydroxyl groups, at least one of the hydroxyl groups being substituted by a mono- or polyalkoxylated group. Preferably, the surfactants used have a mean degree of alkoxylation ranging from 1 to 80, more preferably from 1 to 50, more preferably from 5 to 25, and advantageously from 10 to 20. Generally, the mono- or poly- Alkoxylates are formed by the reaction of alkylene oxide condensation on the cyclic molecule carrying hydroxyl functions. These may be ethylene oxide, propylene oxide or mixtures of these monomers which form copolymers of ethylene oxide and propylene oxide, optionally block polymers.
    The grafting of alkoxylated groups on the hydroxyl functions can be done by condensation reaction on a hydroxyl function or on several hydroxyl functions of the molecule, depending on the number of hydroxyl groups present, their reactivity, and the reaction conditions. In general, the average degree of alkoxylation is defined as the number of moles of alkylene oxide that has been reacted with the molecule to be grafted.
    The surfactant system may also comprise polyalkylene oxide polymers and copolymers, in particular ethylene polyoxides, propylene polyoxides, copolymers of ethylene oxide and propylene oxide, optionally block polymers, or mixtures of these polymers. These polymers are sometimes formed in parallel with the grafting of the alkylene oxides on the hydroxyl functions of the C4-C20 oxygenated hydrocarbon molecule and remain in a mixture with these. Commercial products of the C4-C20 oxygenated hydrocarbon molecule type carrying hydroxyl functions grafted with alkylene oxides generally comprise minor amounts of these polyalkylene oxide polymers and copolymers.
    The surfactant system may optionally include minor amounts of the fatty acid esters and these polyalkylene oxide polymers and copolymers.
    The number of fatty acid molecules which has reacted with the oxygenated C4-C20 hydrogenated molecule may be greater than 1. The ester may thus be a monoester, a diester, a triester or a tetraester. In the case where the molecule is a polyester, distinct fatty acid groups may have reacted with different hydroxyl groups. Preferably the ester is a monoester.
    The fatty acid moiety of the alkoxylated fatty acid and sorbitan ester may be saturated or unsaturated and may be linear or branched, and its carbon number may be from 8 to 30, preferably from 10 to 24, more preferably For example, the fatty acid may be a saturated fatty acid such as n-caproic acid, caprylic acid, n-capric acid, lauric acid, myristic acid, acid, and the like. palmitic acid, stearic acid, isostearic acid, arachidic acid or unsaturated fatty acid such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid or docosahexaenoic acid. Stearic acid, myristic acid and palmitic acid are examples of preferred fatty acids.
    Advantageously, the invention uses a mixture of fatty acid esters based on a mixture of acids comprising stearic acid, myristic acid and palmitic acid. Preferably, the invention uses a mixture of fatty acid esters based on a mixture of acids consisting of stearic acid, myristic acid and palmitic acid.
    According to this variant, preferably, the nonionic surfactant or surfactants are chosen from mono- or polyalkoxylated fatty acid and sorbitan esters or mono- or polyalkoxylated isosorbide esters.
    Preferably, the mono- or polyalkoxylated fatty acid and sorbitan esters and the mono- or polyalkoxylated isosorbides employed have an average degree of alkoxylation ranging from 1 to 80, more preferably from 1 to 50, advantageously from 5 to 25, and preferably from 10 to 20.
    According to this variant, even more advantageously, the nonionic surfactant or surfactants are chosen from mono- or poly-ethoxylated fatty acid and sorbitan esters or mono- or poly-ethoxylated isosorbide esters.
    These molecules are represented by formulas (ΠΙ) and (IV) below: Esters of fatty acids and of ethoxylated sorbitans:
    (III)
    With m, n, p and q, identical or different, integers ranging from 0 to 20, the sum m + n + p + q ranging from 1 to 80, preferably from 1 to 50. R1, R2, R3, R4 independently represent a hydrogen atom or a C8-C30 alkylcarboxylic group, at least one of R1, R2, R3 and R4 being distinct from H. - Esters of fatty acids and ethoxylated isosorbides:
    (IV)
    With m, n, identical or different, integers ranging from 0 to 20, the sum m + n ranging from 1 to 40; R1, R2 independently represent a hydrogen atom or a C8-C30 alkylcarboxylic group, at least one of R1 and R2 being distinct from H.
    Such molecules are commercially available in particular under the name Polysorbate or under the trade name Radiasurf® sold by Oleon.
    Fatty acid esters and alkoxylated C4-C20 oxygenated hydrocarbon molecules, in particular mono- or poly-ethoxylated fatty acid and sorbitan esters and mono- or poly-ethoxylated isosorbides, and mixtures thereof, are advantageously introduced into the aqueous composition in amounts ranging from 1 to 70% by mass relative to the total weight of paraffins in the composition, better from 1 to 50%, preferably from 5 to 40%, more preferably from 10 to 30% .
    According to this second variant, preferably, the surfactant system consists essentially of:
    One or more esters of fatty acids and oxygenated C4-C20 hydrocarbon molecules comprising one or two furanose or pyranose rings, and one or more hydroxyl groups, at least one of the hydroxyl groups being substituted with a mono- or polyalkoxylated group; .
    Even more preferentially, according to this variant, the surfactant system consists essentially of:
    One or more esters of mono- or poly-ethoxylated fatty acids and sorbitans or mono- or poly-ethoxylated isosorbides.
    Advantageously, according to this variant, the surfactant system consists essentially of:
    One or more molecules chosen from mono- or poly-ethoxylated fatty acid and sorbitan esters of formula (III) or mono- or poly-ethoxylated isosorbides of formula (IV) as defined above. - Third variant:
    According to a preferred embodiment, the composition comprises at least, or better still, consists essentially of: a nonionic surfactant chosen from oxygenated C4-C20 hydrocarbon molecules comprising one or two furanose or pyranose rings, and one or more groups hydroxyls, at least one of the hydroxyl groups being substituted by a mono- or polyalkoxylated group, an emulsion stabilizer chosen in particular from C 8 -C 30 fatty acids, a nonionic surfactant chosen from acid esters, C8-C30 fatty acids and oxygenated C4-C20 hydrocarbon molecules comprising one or two furanose or pyranose rings, and one or more hydroxyl groups, at least one of the hydroxyl groups being substituted with a mono- or polyalkoxylated group.
    Even more preferentially, according to this variant, the composition comprises at least, or better still, consists essentially of: a nonionic surfactant chosen from mono- or poly-ethoxylated sorbitans and mono- or poly-ethoxylated isosorbides, a stabilizer emulsion chosen in particular from C10-C24 fatty acids, - a nonionic surfactant chosen from C10-C24 fatty acid esters and mono- or poly-ethoxylated sorbitans or mono- or poly-ethoxylated isosorbides .
    Advantageously, according to this variant, the composition comprises at least, or better still, consists essentially of: a nonionic surfactant chosen from the mono- or poly-ethoxylated sorbitans of formula (I) and the mono- or poly-ethoxylated isosorbides of formula (Π), - an emulsion stabilizer chosen in particular from C 12 -C 20 fatty acids, - a nonionic surfactant chosen from C 12 -C 20 fatty acid esters and mono- or poly-ethoxylated sorbitans of formula (III) or mono- or poly-ethoxylated isosorbides of formula (IV).
    Possibly, in view of the synthesis process of these molecules, the presence of polymers and copolymers of ethylene oxide and propylene oxide, as well as esters of fatty acids and such polymers may be envisaged.
    The surfactants and stabilizers are used in amounts sufficient to allow the dispersion of the paraffin in the aqueous composition. Those skilled in the art can adapt their dosage depending on the paraffin chosen and its amount in the composition.
    Advantageously, all of the surfactants and stabilizers represent from 1 to 100% by weight relative to the total mass of paraffin (s) in the composition, better still from 5 to 50% by weight. - Fourth variant:
    According to another preferred embodiment, the composition comprises at least, or better still consists essentially of: a nonionic surfactant chosen from oxygenated C4-C20 hydrocarbon molecules comprising one or two furanose or pyranose rings, and one or more hydroxyl groups, at least one of the hydroxyl groups being substituted by a mono- or polyalkoxylated group; an emulsion stabilizer chosen in particular from C 8 -C 30 fatty acids; a nonionic surfactant chosen from esters of C8-C30 fatty acids and oxygenated C4-C20 hydrocarbon molecules comprising one or two furanose or pyranose rings, and one or more hydroxyl groups.
    Even more preferentially, according to this variant, the composition comprises at least, or better still, consists essentially of: a nonionic surfactant chosen from mono- or poly-ethoxylated sorbitans and mono- or poly-ethoxylated isosorbides, a stabilizer emulsion chosen in particular from C10-C24 fatty acids, - a nonionic surfactant chosen from C10-C24 fatty acid esters and sorbitans or isosorbides. Esters of fatty acids and sorbitans:
    They can be represented by the formula (V) below
    (V)
    Wherein R1, R2, R3, R4 are, independently, a hydrogen atom or a C8-C30 alkylcarboxylic group, at least one of R1, R2, R3 and R4 being distinct from H. - Esters of acids fat and isosorbide:
    They can be represented by the formula (VI) below
    (VI) wherein R1, R2 independently represent a hydrogen atom or a C8-C30 alkylcarboxylic group, at least one of R1 and R2 being distinct from H.
    Advantageously, according to this variant, the composition comprises at least, or better still, consists essentially of: a nonionic surfactant chosen from the mono- or poly-ethoxylated sorbitans of formula (I) and the mono- or poly-ethoxylated isosorbides of formula (II), an emulsion stabilizer chosen in particular from C12-C20 fatty acids, a nonionic surfactant chosen from C12-C20 fatty acid esters and sorbitans of formula (V) or from isosorbides of formula (VI).
    Possibly, given the synthesis process of these molecules, the presence of polymers and copolymers of ethylene oxide and propylene oxide may be considered.
    The surfactants and stabilizers are used in amounts sufficient to allow the dispersion of the paraffin in the aqueous composition. Those skilled in the art can adapt their dosage depending on the paraffin chosen and its amount in the composition.
    Advantageously, all of the surfactants and stabilizers represent from 1 to 100% by weight relative to the total mass of the paraffm (s) in the composition, better still from 5 to 50% by mass.
    The composition :
    The aqueous composition may contain one or more other additives than the polyfunctional additives as defined above, such as, for example, cosolvents intended to promote the dissolution of the surfactant (s) in the aqueous composition. The aqueous composition is prepared in the usual manner by mixing its components, preferably at room temperature, typically in a temperature range generally from 10 to 60 ° C.
    Polyfunctional additives soluble in water, more particularly at room temperature, are generally preferred. For reasons of rapid mixing of the constituents of the aqueous solution, it is preferred to avoid the pasty and / or solid components.
    Preferably, the aqueous compositions correspond to the ISO 22241-1 standard with regard to the quantities indicated in Table 1 of the said standard: aldehydes, insoluble matter, phosphate, calcium, iron, copper, zinc, chromium, nickel, aluminum , sodium, potassium. In general, the aqueous compositions contain any element and / or component in an amount such that it is not likely to be a poison of the SCR catalyst.
    According to one variant, the aqueous composition is a concentrated composition comprising the precursor of the said NOx reducing agent, in particular urea, the paraffin (s) and the surfactant (s) and stabilizer (s), in the proportions exposed above which can be diluted with water prior to its implementation.
    According to another variant, the aqueous composition is a composition comprising the precursor of the said NOx reducing agent, in particular urea, the paraffin (s) and the surfactant (s) and stabilizer (s), in the proportions discussed above, the precursor concentration of said NOx reducing agent being that recommended by injection into the SCR system. Such a composition is injected without prior dilution. According to this variant, preferably the aqueous composition is a composition comprising urea, the paraffin (s) and the surfactant (s) and stabilizer (s), in the proportions explained above, the concentration of urea being 32.5%.
    According to another preferred variant, the aqueous composition is prepared from a preformulated aqueous solution of urea, such as for example a commercial composition known as AdBlue® comprising 32.5% by weight of urea, and a preformulated aqueous composition of paraffin (s). According to this variant, the aqueous paraffin composition comprises the paraffin (s) and the surfactant system described above. The aqueous paraffin composition advantageously has a concentration of active substances of 10 to 90% by weight relative to the total weight of the composition, the active ingredients including the paraffin (s) and the surfactant (s) as defined above. above, and in the relative proportions that have been defined above. Preferably, according to this variant, the aqueous paraffin composition has a concentration of active ingredients of 25 to 75% by weight relative to the total mass of the composition. The mixture of the two compositions is made before injection into the SCR system.
    According to this variant, the amounts of paraffin and surfactant being low compared to the rest of the composition, it can be defined as an aqueous composition comprising substantially 32.5% by weight of urea.
    The same approach could be followed from a preformulated aqueous solution of another precursor of said NOx reducing agent.
    According to a preferred embodiment, the composition of the invention consists essentially of: • water, • an NOx reducing agent or a precursor of an NOx reducing agent, • one or more paraffins dispersed in the aqueous phase , said paraffins representing from 50 to 10,000 ppm by weight relative to the weight of NOx reducing agent or relative to the mass of NOx reducing agent precursor, • one or more surfactants and stabilizers of emulsions, together surfactants and emulsion stabilizers representing from 1 to 100% by weight relative to the total mass of paraffin (s) in the composition.
    According to a still more preferred embodiment, the composition of the invention consists essentially of: • water, • urea, • one or more paraffins dispersed in the aqueous phase, said paraffins representing from 50 to 10,000 ppm in mass relative to the mass of urea, • one or more surfactants and stabilizers of emulsions, all of the surfactants and stabilizers of emulsions representing from 1 to 100% by mass relative to the total mass of paraffin (s) in the composition.
    Method of implementation: The invention also relates to the use of the aqueous composition according to the invention in any spraying device for the aftertreatment of exhaust gas, more particularly SCR devices. The invention also relates to a method for treating an exhaust stream of an engine, this process comprising the injection of a composition based on a NOx reducing agent or a precursor of said agent, in particular based on urea, as described above. The injection of the composition of the invention is carried out upstream with respect to the positioning of the SCR device in the exhaust pipe. This process makes it possible to reduce the deposits in the exhaust pipe, in particular the cyanuric acid deposits.
    In addition, compared with compositions of the prior art, the method of the invention allows the handling of the composition, in particular the filling of the tank, without foaming or with reduced foaming.
    Finally, compared with compositions of the prior art, the method of the invention allows a better control of the injected amount of NOx reducing agent or precursor of said agent. Indeed, in the absence of foaming, only the aqueous composition is injected, while some prior compositions, by foaming, promote the injection of air into the tank and cause an imprecise operation of the filling gauge. The invention also relates to the use of a dispersion or an emulsion or an aqueous suspension of paraffin as defined above as an additive in an aqueous solution of a NOx reducing agent, or an aqueous solution of precursor of said agent, in particular in an aqueous solution of urea, for use in an SCR system. This use aims to reduce or avoid deposits in the SCR device while also reducing or preventing the foaming of the aqueous solution of NOx reducing agent during handling, in particular when it is introduced into a tank. This use is also intended to allow better control of the amount of NOx reducing agent or precursor of said injected agent.
    Figures:
    Figure 1: schematic representation of an SCR bench.
    Figure 2: schematic representation of a foaming evaluation device.
    The following examples are given to illustrate the features of the invention but not to limit the scope.
    Experimental part :
    In the experimental part, all the percentages are expressed by weight relative to the total mass of the composition. I-Material and methods: - Preparation of the compositions:
    As a basis for the composition, a commercial aqueous solution of 32.5% by weight of urea: AdBlue® was used.
    This composition was additivated with different compositions in the amounts indicated in Table 2: On the one hand with a paraffin emulsion (Emulsion P), on the other hand with surfactant compositions of the prior art. Emulsion P: aqueous emulsion comprising (in% by weight relative to the total mass of the emulsion) 50% of water, 42% of C22-C32 paraffins, about 8% of a mixture of sorbitans and isosorbides polyoxyethylenated, the distribution of the polyoxyethylenated chains being centered respectively on C13 and C16, of fatty acids consisting of stearic (C18: 0), palmitic (C16: 0) and myristic (C14: 0) acids and stearic esters (C18: 0) and palmitic (C16: 0) sorbitan. Polyaldo ™ TMSH KFG (3-1-SH): product of the reaction of a triglycerol with saturated C16-C18 and unsaturated C18 fatty acids, marketed by the company Lonza - Marlipal 013/30 ®: 13-oxoalcohol (isotridecanol + 3 EO / mol) marketed by Sasol. 70% Marlipal ® 013/120 + 30% Marlipal ® 013/30 mixture (marketed by Sasol): 30% C13-oxoalcohol (isotridecanol + 3 EO / mol) + 70% C13-oxoalcohol (isotridecanol + 12 EO) / mol)
    Radiasurf 7157 ®: ethoxylated sorbitan monostearate (20EO) - HLB = 15 sold by the company Oleon
    Radiasurf 7137 ®: ethoxylated sorbitan monolaurate (20EO) sold by the company Oleon
    Proppabort: alkoxylated fatty alcohol marketed by the company Proppabort AB - Observation and measurement of deposits:
    The tests were carried out on an SCR bench 1 whose configuration is shown in FIG. 1. The composition C is sprayed via an injector 2 located slightly set back with respect to the stream 3 of the exhaust gases. The droplets of solution 4 are then impacted on the mixer 5 to facilitate its homogenization and hydrolysis reaction of urea in the hot gas stream. The exhaust line is supplied with air by a hot air gun (not shown), the temperature of the gases and their flow are controlled. Thermocouples (not shown) placed at the injector at the line exit and close to the line allow monitoring of the thermal conditions during the test.
    The operating conditions of the test are summarized in Table 1 below:
    Table 1: Operating conditions selected for the SCR bench
    In order to evaluate the performance of a product, we compared the mass of deposits collected on the two following zones: the "injector" zone (nose / nozzle holder) and the "mixer" zone (upstream / mixer / downstream) .
    The deposits were thus collected and weighed on the "injector" and "mixer" areas of the SCR line. Total deposits collected for each trial were calculated. - Evaluation of foaming:
    The method is based on the use of a device 10 comprising a reservoir 11 (injection column) in which the product 12 is kept under pressure, a 250 ml graduated glass test piece 13, a photoelectric type detection cell 14 , a solenoid valve 15 controlling the opening and closing of the reservoir and a stopwatch (not shown). The method consists of injecting a quantity of product 12 (100 ml) at a pressure of 400 millibars into the graduated cylinder 13. The detection cell 14 detects when the 100 ml of product 12 initially present in the injection column 11 were emptied into the test tube 13. The solenoid valve 15 closes and the timer is triggered. The volume of foam formed is visually identified using the graduations 16 present on the specimen 13. The time after which the foam has completely disappeared is also noted. The test is stopped after 300 seconds if foam is still present.
    II- Tests:
    The tests carried out are reported in Table 2 below. The reference example was made with a commercial 32% commercial urea solution AdBlue ®. The other examples were carried out with the same 32% commercial aqueous AdBlue® solution of urea to which the various additives mentioned were added. Tests C1 and C2 are according to the invention. Tests DI to D6 are comparative.
    Table 2: Formulations made (*) ADBLUE ® 32.5% aqueous solution of urea
    III- Results:
    The test results are reported in Table 3 below:
    Table 3: Test results
    It is found that the examples according to the invention C1 and C2 have a reduced amount of deposits compared to the reference and compared to most of the comparative examples (D2 to D6). In addition, the examples according to the invention have little foaming, and it disappears quickly, unlike the compositions of the prior art.
    权利要求:
    Claims (22)
    [1" id="c-fr-0001]
    An aqueous composition comprising at least one NOx reducing agent or a precursor of a NOx reducing agent, characterized in that it comprises at least one paraffin dispersed in the aqueous phase, said paraffin representing from 50 to 10,000 ppm by weight relative to the NOx reducing agent mass or the NOx reducing agent precursor mass.
    [2" id="c-fr-0002]
    2. Composition according to claim 1 wherein the precursor of the NOx reducing agent is urea.
    [3" id="c-fr-0003]
    3. Composition according to any one of the preceding claims, wherein the C20-C36 paraffins represent at least 90% by weight relative to the total weight of paraffins in the composition.
    [4" id="c-fr-0004]
    4. Composition according to any one of the preceding claims, which comprises at least one surfactant, and optionally an emulsion stabilizing agent.
    [5" id="c-fr-0005]
    The composition of claim 4 which comprises at least one nonionic surfactant.
    [6" id="c-fr-0006]
    6. The composition according to claim 5, which comprises at least one nonionic surfactant chosen from oxygenated C4-C20 hydrocarbon molecules comprising one or two furanose or pyranose rings, and one or more hydroxyl groups, at least one of the hydroxyl groups being substituted with a mono- or polyalkoxylated group.
    [7" id="c-fr-0007]
    The composition of claim 6 wherein the nonionic surfactant is selected from polyethoxylated sorbitans and polyethoxylated isosorbides.
    [8" id="c-fr-0008]
    8. Composition according to any one of claims 6 and 7 wherein the C4-C20 oxygenated hydrocarbon surfactants comprising one or two furanose or pyranose rings, and one or more hydroxyl groups, mono- or poly-alkoxylated, are present in amounts ranging from 1 to at 70% by weight relative to the total mass of paraffins in the composition.
    [9" id="c-fr-0009]
    9. Composition according to any one of claims 4 to 8, which further comprises at least one emulsion stabilizing agent selected from fatty acids.
    [10" id="c-fr-0010]
    10. Composition according to claim 9 wherein the fatty acid is present in amounts ranging from 1 to 50% by weight relative to the total weight of paraffins in the composition.
    [11" id="c-fr-0011]
    11. A composition according to claim 5 which comprises at least one nonionic surfactant selected from esters of fatty acids and oxygenated C4-C20 hydrocarbon molecules comprising one or two furanose or pyranose rings, and one or more hydroxyl groups, one to the less hydroxyl groups being substituted by a mono- or polyalkoxylated group.
    [12" id="c-fr-0012]
    12. Composition according to claim 11, in which the nonionic surfactant or surfactants are chosen from mono- or poly-ethoxylated fatty acid and sorbitan esters and mono or poly isosorbide and fatty acid esters. -éthoxylés.
    [13" id="c-fr-0013]
    13. Composition according to any one of claims 11 and 12, wherein the esters of fatty acids and C4-C20 oxygenated hydrocarbon molecules comprising one or two rings furanose or pyranose, and one or more hydroxyl groups, mono or poly -alkoxylated, are present in amounts ranging from 1 to 70% by mass relative to the total mass of paraffins in the composition.
    [14" id="c-fr-0014]
    14. Composition according to any one of claims 4 to 13, which comprises at least: a nonionic surfactant chosen from C4-C20 oxygenated hydrocarbon molecules comprising one or two furanose or pyranose rings, and one or more hydroxyl groups; at least one of the hydroxyl groups being substituted by a mono- or polyalkoxylated group, an emulsion stabilizer chosen in particular from C 8 -C 30 fatty acids, and a nonionic surfactant chosen from acid esters. and one or two furanose or pyranose rings, and one or more hydroxyl groups, at least one of the hydroxyl groups being substituted with a mono- or polyalkoxylated group.
    [15" id="c-fr-0015]
    15. Composition according to any one of claims 4 to 10, which comprises at least: a nonionic surfactant chosen from C4-C20 oxygenated hydrocarbon molecules comprising one or two furanose or pyranose rings, and one or more hydroxyl groups; at least one of the hydroxyl groups being substituted by a mono- or polyalkoxylated group, an emulsion stabilizer chosen in particular from C 8 -C 30 fatty acids, and a nonionic surfactant chosen from acid esters. and oxygenated C4-C20 hydrocarbon molecules comprising one or two furanose or pyranose rings, and one or more hydroxyl groups.
    [16" id="c-fr-0016]
    16. Composition according to any one of claims 4 to 15, wherein the set of surfactants and emulsion stabilizers is 1 to 100% by mass relative to the total weight of paraffin (s) in the composition.
    [17" id="c-fr-0017]
    17. Use of a composition according to any one of claims 1 to 16, for the aftertreatment of the exhaust gas by Selective Catalytic Reductant catalyst.
    [18" id="c-fr-0018]
    18. Use according to claim 17, to prevent, limit, prevent the formation of deposits in an exhaust line SCR.
    18. Use of a composition according to any one of claims 1 to 16, to prevent or reduce foaming during filling of a reservoir by the composition.
    [19" id="c-fr-0019]
    19. Process for treating exhaust gases in an internal combustion engine, preferably a diesel engine equipped with an SCR system, this method being characterized in that it comprises at least one step of introducing a composition. according to any one of claims 1 to 16 in the SCR line, upstream of the SCR system.
    [20" id="c-fr-0020]
    20. Process for reducing deposits in an SCR line, this method being characterized in that it comprises at least one step of introducing a composition according to any one of Claims 1 to 16 into the SCR line, upstream. of the SCR system.
    [21" id="c-fr-0021]
    21. The method of claim 19 or claim 20, which comprises a step of preparing an aqueous composition of a NOx reducing agent, or a precursor of a NOx reducing agent, and paraffin (s). ) according to any one of claims 1 to 16.
    [22" id="c-fr-0022]
    22. Use of an emulsion or dispersion or an aqueous suspension of paraffin as an additive in an aqueous solution of a NOx reducing agent or a NOx reducing agent precursor, for the purpose of an implementation in an SCR system.
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    同族专利:
    公开号 | 公开日
    US10399035B2|2019-09-03|
    EP3383522B1|2020-06-24|
    FR3044564B1|2021-01-22|
    PT3383522T|2020-09-22|
    WO2017093644A1|2017-06-08|
    ES2815538T3|2021-03-30|
    EP3383522A1|2018-10-10|
    CA3006335A1|2017-06-08|
    US20180353904A1|2018-12-13|
    JP2019503843A|2019-02-14|
    PL3383522T3|2020-12-14|
    BR112018011284A2|2018-11-27|
    CN108367239A|2018-08-03|
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    法律状态:
    2016-11-21| PLFP| Fee payment|Year of fee payment: 2 |
    2017-06-09| PLSC| Publication of the preliminary search report|Effective date: 20170609 |
    2017-11-21| PLFP| Fee payment|Year of fee payment: 3 |
    2019-11-20| PLFP| Fee payment|Year of fee payment: 5 |
    2020-11-20| PLFP| Fee payment|Year of fee payment: 6 |
    2021-12-24| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1561762A|FR3044564B1|2015-12-02|2015-12-02|UREA-BASED COMPOSITION FOR THE TREATMENT OF EXHAUST GASES|FR1561762A| FR3044564B1|2015-12-02|2015-12-02|UREA-BASED COMPOSITION FOR THE TREATMENT OF EXHAUST GASES|
    CA3006335A| CA3006335A1|2015-12-02|2016-11-28|Composition made from urea for treating exhaust gases|
    PT168167245T| PT3383522T|2015-12-02|2016-11-28|Composition made from urea for treating exhaust gases|
    JP2018528336A| JP2019503843A|2015-12-02|2016-11-28|Composition made from urea to treat exhaust gas|
    US15/778,604| US10399035B2|2015-12-02|2016-11-28|Composition made from urea for treating exhaust gases|
    PL16816724T| PL3383522T3|2015-12-02|2016-11-28|Composition made from urea for treating exhaust gases|
    EP16816724.5A| EP3383522B1|2015-12-02|2016-11-28|Composition made from urea for treating exhaust gases|
    BR112018011284-4A| BR112018011284A2|2015-12-02|2016-11-28|"composition made of urea for the treatment of exhaust gases"|
    ES16816724T| ES2815538T3|2015-12-02|2016-11-28|Urea-based composition for exhaust gas treatment|
    CN201680070942.4A| CN108367239A|2015-12-02|2016-11-28|The composition prepared by urea for handling exhaust gas|
    PCT/FR2016/053118| WO2017093644A1|2015-12-02|2016-11-28|Composition made from urea for treating exhaust gases|
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