EP3374062A1 - Fluid for purifying heat engines and methods for preparing said fluids by emulsification - Google Patents

Fluid for purifying heat engines and methods for preparing said fluids by emulsification

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Publication number
EP3374062A1
EP3374062A1 EP16784197.2A EP16784197A EP3374062A1 EP 3374062 A1 EP3374062 A1 EP 3374062A1 EP 16784197 A EP16784197 A EP 16784197A EP 3374062 A1 EP3374062 A1 EP 3374062A1
Authority
EP
European Patent Office
Prior art keywords
fluid
depollution
heat engines
surfactant
precursor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP16784197.2A
Other languages
German (de)
French (fr)
Inventor
Christine Dalmazzone
Stéphane RAUX
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
IFP Energies Nouvelles IFPEN
Original Assignee
IFP Energies Nouvelles IFPEN
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by IFP Energies Nouvelles IFPEN filed Critical IFP Energies Nouvelles IFPEN
Publication of EP3374062A1 publication Critical patent/EP3374062A1/en
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/90—Injecting reactants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/023—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles
    • F01N3/029—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles by adding non-fuel substances to exhaust
    • F01N3/0293—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles by adding non-fuel substances to exhaust injecting substances in exhaust stream
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/66—Regeneration of the filtering material or filter elements inside the filter
    • B01D46/80—Chemical processes for the removal of the retained particles, e.g. by burning
    • B01D46/82—Chemical processes for the removal of the retained particles, e.g. by burning with catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
    • B01D53/9477—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on separate bricks, e.g. exhaust systems
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/2066—Selective catalytic reduction [SCR]
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2896—Liquid catalyst carrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2065—Ammonium hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2067—Urea
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/21—Organic compounds not provided for in groups B01D2251/206 or B01D2251/208
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/302—Alkali metal compounds of lithium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/80—Organic bases or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/906—Catalyst dispersed in the gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B01D2258/012—Diesel engines and lean burn gasoline engines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2279/00—Filters adapted for separating dispersed particles from gases or vapours specially modified for specific uses
    • B01D2279/30—Filters adapted for separating dispersed particles from gases or vapours specially modified for specific uses for treatment of exhaust gases from IC Engines
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/01—Adding substances to exhaust gases the substance being catalytic material in liquid form
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/02—Adding substances to exhaust gases the substance being ammonia or urea
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/03—Adding substances to exhaust gases the substance being hydrocarbons, e.g. engine fuel
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention describes a unique fluid for automotive pollution control, enabling two distinct operations to be carried out: the selective catalytic reduction of NOx using Selective Catalytic Reduction technology, commonly referred to by its English name Selective Catalytic Reduction, or by the acronym SCR, as well as the aid for the regeneration of the particulate filter (DPF), this regeneration aid being able to be manifested either by the promotion of the continuous regeneration of the particle filter, or by the acceleration of the combustion of the soot during active regeneration phases of the FAP, either by a combination of these two advantages.
  • the fluid according to the invention has a homogeneous appearance and exhibits stability characteristics over time, or during variations in temperature or pH.
  • the present invention describes different modes of obtaining the fluid as well as the mode of use of this fluid.
  • AdBlue ® (or AUS32 or DEF or ARLA32) is a 32.5% by weight urea solution in pure water, which is used for the selective reduction of nitrogen oxides as part of the technology. SCR for road and non-road applications.
  • Eolys Powerflex ® , Infineum F7995 ® or Tenneco Walker ® are additives consisting of an organic colloidal dispersion of metal particles in a mixture hydrocarbons (described for the Eolys in the texts FR 2833862 and FR 2969653 Bl) intended to assist the regeneration of the FAP and allow oxidation of soot at a lower temperature.
  • the present invention describes a fluid for the depollution of heat engines, in particular diesel engines, making it possible to carry out both the selective catalytic reduction of the nitrogen oxides contained in the exhaust gas (so-called SCR function), as well as the assistance to the regeneration of the particulate filter (FAP) by catalytic combustion of soot particles deposited in the particulate filter (so-called FAP regeneration aid function), this regeneration aid being able to be manifested either by the promotion of the regeneration continuous particle filter, either by accelerating the combustion of soot during active regeneration phases of FAP, or a combination of these two advantages.
  • SCR function selective catalytic reduction of the nitrogen oxides contained in the exhaust gas
  • FAP regeneration aid function catalytic combustion of soot particles deposited in the particulate filter
  • soot oxidation catalyst differs from the previously cited prior art in that it is injected directly into the exhaust thus not passing through the combustion chamber of the engine.
  • the injection of the fluid according to the invention is triggered by the engine computer to meet a need to have the necessary amount of ammonia on the SCR catalyst to operate the effective reduction of NOx.
  • the injections are carried out regularly, in a period typically between a few milliseconds and a few tens of seconds depending on the operating conditions of the engine, which allows to promote a homogeneous mixture of the catalyst with the soot and to ensure an intimate contact between soot and catalyst.
  • the fact of injecting the fluid according to the invention makes it possible either to promote the phenomenon of continuous regeneration of the particulate filter and thus to space the active regeneration periods of the FAP, ie to accelerate the combustion of the soot during active regeneration phases of the FAP, making it possible to limit the fuel consumption relative to this phase and / or to maximize the chances of burning a large soot mass when the conditions temperature and gas composition at the exhaust are favorable to this active regeneration, a combination of these two advantages.
  • the fluid according to the invention is made from a stable mixture of two products immiscible with each other, namely on the one hand an aqueous solution of at least one reducing compound or precursor of a reducing agent such as urea, and on the other hand a dispersion of one or more metal oxides in a hydrocarbon or a mixture of hydrocarbons.
  • a reducing compound or precursor of a reducing agent such as urea
  • a dispersion of one or more metal oxides in a hydrocarbon or a mixture of hydrocarbons a dispersion of one or more metal oxides in a hydrocarbon or a mixture of hydrocarbons.
  • the fluid according to the invention consists of a solution of homogeneous appearance of at least one reducing compound or precursor of a reducing agent, a dispersion of metal oxides, and a surfactant or a mixture surfactants for the manufacture and stabilization of a direct emulsion of the oil-in-water type.
  • the metal (s) making up the metal oxide (s) are chosen from the following metals: Fe, Cu, Ni, Co, Zn, Mn, Ti, V, Sr, Pt, Ce, Ca, Li, Na, Nb.
  • the metals are chosen from the following list: Fe, Ce, Cu, Sr.
  • the dispersion of metal oxides is in the form of a dispersion of one or more iron oxides in an Eolys Powerflex® type hydrocarbon mixture.
  • the reducing compound or precursor of a reducing agent in solution in pure water is selected from urea, ammonia, formamide, and ammonium salts, especially ammonium formate, ammonium carbamate, guanidine salts, especially guanidinium formate.
  • the concentration of metal oxide or metal oxides in the emulsion produced by means of the surfactant (s) with the reducing compound or precursor of a reducing agent is between 10 and 10,000 ppm, preferably between 10 and 5000 ppm. and in a preferred manner between 10 and 2000 ppm.
  • HLB hydrophilic / lipophilic balance
  • the HLB classification is established by the ratio between the fatty chain and the water-soluble group and varies between 0 (completely lipophilic) and 20 (completely hydrophilic).
  • nonionic surfactants will be used.
  • the surfactants are chosen from any commercial formulation or any mixture made from chemical families such as ethoxylated or non-ethoxylated sorbitan esters (such as Tween® and Span® from CRODA), ethylene oxide copolymer blocks ( EO) / propylene oxide (OP) (such as Synperonic®PEL from CRODA), alcohols or ethoxylated fatty acids (such as Simulsol® ox from SEPPIC or Solvay's Rhodasurf®), ethoxylated fatty acid esters (such as CRODA's Atlas®), ethoxylated octylphenols (such as Union Carbide TRITON® X), alkylpolyglucosides or APGs (such as Simulsol SL® from SEPPIC and Plantacare 2000 UP® from BASF) alone or as a mixture.
  • chemical families such as ethoxylated or non-ethoxylated sorbitan esters (such as T
  • the reducing compound (s) or the precursor (s) of a reducing agent is urea at 32.5 ⁇ 0.7% by weight in solution in demineralised water or pure water, meeting the specifications of ISO 22241
  • the solution containing the reducing compound (s) or the precursor (s) of a reducing agent of the reducing compound is prepared from a product meeting the specifications of the ISO 22241 standard, for example commercial products AdBlue®, DEF, AUS32 or ARLA32.
  • the solution containing the reducing compound (s) or the precursor (s) of a reducing agent is prepared from a product that complies with the physical and chemical characteristics of the ISO 22241-1 standard, for example the commercial product Diaxol®.
  • Adblue® will be used to refer to the following products: Adblue®, DEF, AUS32, ARLA32 or Diaxol®.
  • the fluid for the depollution of heat engines according to the invention preferably remains stable in a temperature range of -11 to + 60 ° C.
  • the fluid for the depollution of heat engines has good stability with respect to light.
  • the present invention also relates to different embodiments of the fluid for the depollution of heat engines.
  • a surfactant is added to a solution of at least one reducing compound or precursor of a reducing agent, and then the dispersion of metal oxides which is emulsified by means of a system is added. suitable mixture, and then diluted with a solution addition of at least one reducing compound or precursor of a reducing agent to achieve the desired metal oxide content.
  • a surfactant is added in a solution of at least one reducing compound or precursor of a reducing agent, and then the dispersion of metal oxides is added. emulsion by means of a suitable mixing system so as to obtain directly the desired metal oxide content.
  • the present invention also relates to the use of the depollution fluid in a diesel-type internal combustion engine, the injection of said fluid being carried out upstream of the exhaust gas treatment systems SCR and FAP, (or the single treatment system when grouped into a single module), and being operated regularly according to the operating conditions of the engine.
  • the invention consists of a multifunctional fluid for the depollution of exhaust gases from an internal combustion engine.
  • the multifunctional fluid according to the invention promotes either the continuous regeneration of the particulate filter or the combustion of soot during the active regeneration phases of the FAP, or allows a combination of these two advantages.
  • This fluid consists essentially of an emulsion between a dispersion of one or more metal oxides in a hydrocarbon or a mixture of hydrocarbons on the one hand, and an aqueous solution containing at least one reducing agent or at least one agent precursor NOx reducer on the other hand.
  • Said emulsion is made possible by the presence of one or more surfactants.
  • the fluid thus obtained makes it possible to concomitantly perform two functions necessary for the depollution of the thermal engines, more particularly of the diesel engine, the reduction catalytic selective NOx and aid in the oxidation of particles trapped in the FAP by catalytic combustion.
  • the production of the fluid according to the invention leads to an emulsion which has stability characteristics over time, up to a temperature of 60.degree.
  • the fluid according to the invention can be made from a commercial solution of AdBlue ® according to ISO 22241 specifications.
  • An important advantage of the fluid according to the invention lies in the fact that it combines the two functions of decontamination of engine emissions in a single fluid.
  • One of the other advantages of the invention is not to substantially modify the density, viscosity and retention properties of the AdBlue ® solution, which means in practice that no modification of the AdBlue injection system ® in the engine is necessary in order to benefit from the advantages of the invention.
  • the principle of the invention is to combine in a single fluid on the one hand a reducing agent or reducing agent precursor, such as urea, which will act as a reducing agent, or as a reducing agent precursor such as ammonia, and secondly a dispersion of metal oxides which, in the exhaust line under the effect of the temperature and the residual oxygen of the exhaust gas, will put soot in contact with a the compound lowers their oxidation temperature, which has the effect of aiding in the continuous oxidation of the filtered soot and reducing the energy cost of active regeneration of the filter when it is necessary.
  • Another effect of the metal oxides is to increase the rate of oxidation of soot by a catalytic process and thus regenerate the FAP in a reduced time.
  • the simplest is to modify a commercial solution of AdBlue ® or to make a solution of urea according to ISO 22241 specifications, or even to use another reducing compound such as ammonia for example.
  • Surfactants are numerous. They can be dissociated into cationic, anionic and nonionic surfactants.
  • the emulsification (that is to say the process of dispersion of oil in water) can be carried out by any appropriate means using any batch dynamic mixer or continuous known to those skilled in the art .
  • Devices of this type are, for example, rotor and stator mixers (for example those marketed by Rayneri under the brand name Ultramix®), colloid mills, high-pressure homogenizers or ultrasound devices.
  • rotor and stator mixers for example those marketed by Rayneri under the brand name Ultramix®
  • colloid mills for example those marketed by Rayneri under the brand name Ultramix®
  • high-pressure homogenizers for example, high-pressure homogenizers or ultrasound devices.
  • the content of metal oxides in the final composition of the fluid according to the invention may be between 1 and 10,000 ppm, preferably between 1 and 5000 ppm, and more preferably between 10 and 2000 ppm.
  • the reduction of the metal content makes it possible to limit the accumulation of metallic ash in the FAP.
  • the fluid as described in the present invention is stable over time.
  • the action of light does not alter the stability of the emulsion, and the conditions of crystallization and stability of urea are not affected.
  • the inventive nature of the invention lies in the judicious selection of the components of the formulation. It is not easy to produce a stable emulsion between, on the one hand, a dispersion of metal oxides in one or more hydrocarbons, and, on the other hand, an aqueous solution of urea. Indeed, of course, these two phases, one aqueous, the other oily, are immiscible.
  • the fluid can be prepared at room temperature or at a temperature below 60 ° C. When the fluid has two distinct phases, it does not meet the specifications.
  • the fluid is produced as follows: 51 g of AdBlue ® are introduced into a 150 cm glass flask, a mass of surfactant of 1.5 grams is added and dispersed by means of a manual stirrer. Then introduced 3 g of Eolys Powerflex ® is dispersed using a laboratory mixer provided with a blade adapted to the formation of an emulsion. After stirring for 5 minutes at room temperature, the appearance of the fluid is evaluated.
  • the fluid is produced as follows: 100 g of AdBlue ® are added to a 250 cm glass flask and a mass of 1 gram surfactant is added and dispersed by means of a manual stirrer. Then added 2 g of Eolys Powerflex ® is dispersed using a laboratory mixer provided with a blade adapted to the formation of an emulsion. After stirring for 15 minutes at room temperature, the appearance of the fluid obtained is evaluated.
  • Example 4 does not satisfy the invention because they lead to a heterogeneous fluid.
  • Example 5 satisfies the criteria of the invention.
  • Table 3 Evaluation of the characteristics of different fluids according to the invention at a temperature close to that of crystallization of AdBlue

Abstract

The present invention describes a fluid suitable for purifying heat engines making it possible to both carry out catalytic reduction of the nitrogen oxides (DeNOx) contained in the exhaust gases and help regenerate the particle filter (FAP). The invention also describes several methods for obtaining said fluid consisting of producing an oil-in-water emulsion.

Description

FLUIDE POUR LA DEPOLLUTION DES MOTEURS THERMIQUES ET MODES DE PREPARATION DESDITS FLUIDES PAR EMULSIFICATION FLUID FOR THE DEPOLLUTION OF HEAT ENGINES AND METHODS OF PREPARATION OF SAID FLUIDS BY EMULSIFICATION
CONTEXTE DE L'INVENTION BACKGROUND OF THE INVENTION
La présente invention décrit un fluide unique pour la dépollution automobile, permettant d'effectuer deux opérations distinctes : la réduction catalytique sélective des NOx en utilisant la technologie de Réduction Catalytique Sélective, couramment désignée par son nom anglais Sélective Catalytic Réduction, ou par l'acronyme SCR, ainsi que l'aide à la régénération du filtre à particules (FAP), cette aide à la régénération pouvant se manifester soit par la promotion de la régénération en continu du filtre à particules, soit par l'accélération de la combustion des suies lors des phases de régénération actives du FAP, soit par une combinaison de ces deux avantages. Le fluide selon l'invention est d'aspect homogène et présente des caractéristiques de stabilité dans le temps, ou lors de variations de la température ou de pH. La présente invention décrit différents modes d'obtention du fluide ainsi que le mode d'utilisation de ce fluide.  The present invention describes a unique fluid for automotive pollution control, enabling two distinct operations to be carried out: the selective catalytic reduction of NOx using Selective Catalytic Reduction technology, commonly referred to by its English name Selective Catalytic Reduction, or by the acronym SCR, as well as the aid for the regeneration of the particulate filter (DPF), this regeneration aid being able to be manifested either by the promotion of the continuous regeneration of the particle filter, or by the acceleration of the combustion of the soot during active regeneration phases of the FAP, either by a combination of these two advantages. The fluid according to the invention has a homogeneous appearance and exhibits stability characteristics over time, or during variations in temperature or pH. The present invention describes different modes of obtaining the fluid as well as the mode of use of this fluid.
EXAMEN DE L'ART ANTERIEUR EXAMINATION OF THE PRIOR ART
Différentes technologies sont mises en œuvre pour diminuer les émissions nocives des gaz d'échappement issus des moteurs thermiques Diesel, notamment les oxydes d'azote (NOx) et les particules.  Different technologies are implemented to reduce the harmful emissions of diesel engine exhaust fumes, including nitrogen oxides (NOx) and particulate matter.
Un exemple de ligne d'échappement intégrant le système de traitement deNOx par réduction catalytique sélective, (notée SCR abréviation de Sélective Catalytic Réduction dans la terminologie anglo saxonne), et le filtre à particules (en abrégé FAP), est donné dans le brevet FR 2947004. Ces deux systèmes de dépollution peuvent également être regroupés dans un seul module, celui-ci étant connu sous le terme de SCR sur filtre ou SCRF ou SDPF ou SCRoF. An example of an exhaust system integrating the NOx treatment system by selective catalytic reduction, (SCR abbreviation of Selective Catalytic Reduction in the English terminology), and the particulate filter (abbreviated FAP), is given in the patent FR 2947004. These two systems of pollution can also be grouped in a single module, this one being known under the term of SCR on filter or SCRF or SDPF or SCRoF.
Nous n'avons pas trouvé dans la littérature de fluide permettant de cumuler les fonctions de réduction des oxydes d'azote et d'aide à la régénération des particules de suies piégées.  We did not find in the literature of fluid allowing to cumulate the functions of reduction of the oxides of nitrogen and help with the regeneration of the particles of trapped soot.
L'AdBlue® (ou AUS32 ou DEF ou ARLA32) est une solution d'urée à 32,5 % en masse dans de l'eau pure, qui est utilisée pour la réduction sélective des oxydes d'azote dans le cadre de la technologie SCR pour les applications routières et non routières. AdBlue ® (or AUS32 or DEF or ARLA32) is a 32.5% by weight urea solution in pure water, which is used for the selective reduction of nitrogen oxides as part of the technology. SCR for road and non-road applications.
L'Eolys Powerflex®, l'Infineum F7995® ou le Tenneco Walker® sont des additifs constitués d'une dispersion colloïdale organique de particules métalliques dans un mélange d'hydrocarbures (décrit pour l'Eolys dans les textes FR 2833862 et FR 2969653 Bl) destinés à assister la régénération du FAP et permettre une oxydation des suies à plus basse température. Eolys Powerflex ® , Infineum F7995 ® or Tenneco Walker ® are additives consisting of an organic colloidal dispersion of metal particles in a mixture hydrocarbons (described for the Eolys in the texts FR 2833862 and FR 2969653 Bl) intended to assist the regeneration of the FAP and allow oxidation of soot at a lower temperature.
Le concept général de mutualisation de ces fonctions de dépollution a fait l'objet, fin 2014, du dépôt de la demande de brevet français 14/62.228. On peut considérer la présente demande comme un perfectionnement de la demande 14/62.228.  The general concept of pooling these depollution functions was the subject, at the end of 2014, of the filing of the French patent application 14 / 62.228. This application can be considered as a refinement of the application 14 / 62.228.
DESCRIPTION SOMMAIRE DE L'INVENTION SUMMARY DESCRIPTION OF THE INVENTION
La présente invention décrit un fluide pour la dépollution de moteurs thermiques notamment Diesel, permettant d'effectuer à la fois la réduction catalytique sélective des oxydes d'azote contenus dans les gaz d'échappement (fonction dite SCR), ainsi que l'aide à la régénération du filtre à particules (FAP) par combustion catalytique des particules de suies déposées dans le filtre à particules (fonction dite d'aide à la régénération du FAP), cette aide à la régénération pouvant se manifester soit par la promotion de la régénération en continu du filtre à particules, soit par l'accélération de la combustion des suies lors des phases de régénération actives du FAP, soit par une combinaison de ces deux avantages.  The present invention describes a fluid for the depollution of heat engines, in particular diesel engines, making it possible to carry out both the selective catalytic reduction of the nitrogen oxides contained in the exhaust gas (so-called SCR function), as well as the assistance to the regeneration of the particulate filter (FAP) by catalytic combustion of soot particles deposited in the particulate filter (so-called FAP regeneration aid function), this regeneration aid being able to be manifested either by the promotion of the regeneration continuous particle filter, either by accelerating the combustion of soot during active regeneration phases of FAP, or a combination of these two advantages.
L'utilisation du catalyseur d'oxydation des suies diffère de l'art antérieur précédemment cité en ce qu'il est injecté directement à l'échappement ne passant ainsi pas par la chambre de combustion du moteur. The use of the soot oxidation catalyst differs from the previously cited prior art in that it is injected directly into the exhaust thus not passing through the combustion chamber of the engine.
L'injection du fluide selon l'invention est déclenchée par le calculateur moteur pour répondre à un besoin de disposer de la quantité nécessaire d'ammoniac sur le catalyseur SCR pour opérer la réduction efficace des NOx. The injection of the fluid according to the invention is triggered by the engine computer to meet a need to have the necessary amount of ammonia on the SCR catalyst to operate the effective reduction of NOx.
Les injections sont réalisées de manière régulière, selon une période typiquement comprise entre quelques millisecondes et quelques dizaines de secondes dépendant des conditions de fonctionnement du moteur, ce qui permet de favoriser un mélange homogène du catalyseur avec les suies et d'assurer un contact intime entre les suies et le catalyseur.  The injections are carried out regularly, in a period typically between a few milliseconds and a few tens of seconds depending on the operating conditions of the engine, which allows to promote a homogeneous mixture of the catalyst with the soot and to ensure an intimate contact between soot and catalyst.
In fine le fait d'injecter le fluide selon l'invention permet soit de favoriser le phénomène de régénération en continu du filtre à particules et d'espacer ainsi les périodes de régénération actives du FAP, soit d'accélérer la combustion de la suie lors des phases de régénération actives du FAP, permettant de limiter la consommation de carburant relative à cette phase et/ou de maximiser les chances de brûler une masse de suie importante lorsque les conditions de températures et de composition gazeuse à l'échappement sont favorables à cette régénération active, soit une combinaison de ces deux avantages. In fine, the fact of injecting the fluid according to the invention makes it possible either to promote the phenomenon of continuous regeneration of the particulate filter and thus to space the active regeneration periods of the FAP, ie to accelerate the combustion of the soot during active regeneration phases of the FAP, making it possible to limit the fuel consumption relative to this phase and / or to maximize the chances of burning a large soot mass when the conditions temperature and gas composition at the exhaust are favorable to this active regeneration, a combination of these two advantages.
Le fluide selon l'invention est réalisé à partir d'un mélange stable de deux produits non miscibles entre eux, à savoir d'une part une solution aqueuse d'au moins un composé réducteur ou précurseur d'un agent réducteur tels que l'urée, et d'autre part une dispersion d'un ou plusieurs oxydes métalliques dans un hydrocarbure ou un mélange d'hydrocarbures. Dans la suite du texte pour désigner le composant composé d'un ou plusieurs oxydes métalliques dispersé dans un hydrocarbure ou un mélange d'hydrocarbures, nous parlerons de manière abrégée de dispersion d'oxydes métalliques. Le pluriel dans l'expression oxydes métalliques signifie qu'il peut y avoir un ou plusieurs oxydes métalliques en mélange.  The fluid according to the invention is made from a stable mixture of two products immiscible with each other, namely on the one hand an aqueous solution of at least one reducing compound or precursor of a reducing agent such as urea, and on the other hand a dispersion of one or more metal oxides in a hydrocarbon or a mixture of hydrocarbons. In the rest of the text to designate the component composed of one or more metal oxides dispersed in a hydrocarbon or a mixture of hydrocarbons, we will speak in an abbreviated manner of dispersion of metal oxides. The plural in the expression metal oxides means that there may be one or more mixed metal oxides.
Le fluide selon l'invention est constitué d'une solution d'aspect homogène d'au moins un composé réducteur ou précurseur d'un agent réducteur, d'une dispersion d'oxydes métalliques, et d'un tensioactif ou d'un mélange de tensioactifs permettant la fabrication et la stabilisation d'une émulsion directe du type huile dans eau. Le ou les métaux composant le ou les oxydes métalliques sont choisis dans la liste de métaux suivants: Fe, Cu, Ni, Co, Zn, Mn, Ti, V, Sr, Pt, Ce, Ca, Li, Na, Nb.  The fluid according to the invention consists of a solution of homogeneous appearance of at least one reducing compound or precursor of a reducing agent, a dispersion of metal oxides, and a surfactant or a mixture surfactants for the manufacture and stabilization of a direct emulsion of the oil-in-water type. The metal (s) making up the metal oxide (s) are chosen from the following metals: Fe, Cu, Ni, Co, Zn, Mn, Ti, V, Sr, Pt, Ce, Ca, Li, Na, Nb.
De manière préférée, les métaux sont choisis dans la liste suivante : Fe, Ce, Cu, Sr.  Preferably, the metals are chosen from the following list: Fe, Ce, Cu, Sr.
Selon une variante préférée de l'invention, la dispersion d'oxydes métalliques se présente sous forme de dispersion d'un ou plusieurs oxydes de fer dans un mélange d'hydrocarbures de type Eolys Powerflex®.  According to a preferred variant of the invention, the dispersion of metal oxides is in the form of a dispersion of one or more iron oxides in an Eolys Powerflex® type hydrocarbon mixture.
De manière préférée, le composé réducteur ou précurseur d'un agent réducteur en solution dans de l'eau pure est sélectionné parmi l'urée, l'ammoniaque, le formamide, et les sels d'ammonium, notamment le formiate d'ammonium, le carbamate d'ammonium, les sels de guanidine, notamment le formiate de guanidinium.  Preferably, the reducing compound or precursor of a reducing agent in solution in pure water is selected from urea, ammonia, formamide, and ammonium salts, especially ammonium formate, ammonium carbamate, guanidine salts, especially guanidinium formate.
De manière préférée, la concentration en oxyde métallique ou en oxydes métalliques dans l'émulsion réalisée au moyen du ou des tensioactifs avec le composé réducteur ou précurseur d'un agent réducteur est comprise entre 10 et 10000 ppm, de préférence entre 10 et 5000 ppm, et d'une manière préférée entre 10 et 2000 ppm. Preferably, the concentration of metal oxide or metal oxides in the emulsion produced by means of the surfactant (s) with the reducing compound or precursor of a reducing agent is between 10 and 10,000 ppm, preferably between 10 and 5000 ppm. and in a preferred manner between 10 and 2000 ppm.
On peut utiliser pour réaliser l'émulsion tout type de tensioactif, anionique, cationique ou non ionique, de préférence soluble dans l'eau et ayant une HLB (balance hydrophile/lipophile) comprise entre 7 et 16. Adaptée plus spécifiquement aux composés non ioniques, la HLB exprime la relation entre l'hydrophilie et la lipophilie des molécules d'agents de surface. Any type of surfactant, anionic, cationic or nonionic, preferably water-soluble and having an HLB (hydrophilic / lipophilic balance) of between 7 and 16 can be used to make the emulsion. Specifically adapted to nonionic compounds, HLB expresses the relationship between hydrophilicity and lipophilicity of surfactant molecules.
La classification HLB est établie par le rapport entre la chaîne grasse et le groupement soluble dans l'eau et varie entre 0 (complètement lipophile) et 20 (complètement hydrophile).  The HLB classification is established by the ratio between the fatty chain and the water-soluble group and varies between 0 (completely lipophilic) and 20 (completely hydrophilic).
De manière préférée, on utilisera des tensioactifs non ioniques. Preferably, nonionic surfactants will be used.
De manière préférée, les tensioactifs sont choisis parmi toute formulation commerciale ou tout mélange fabriqué à partir de familles chimiques telles que les esters de sorbitan éthoxylés ou non (comme les Tween® et Span® de CRODA), les blocs copolymères oxyde d'éthylène (OE)/oxyde de propylène (OP) (comme les Synperonic®PEL de CRODA), les alcools ou les acides gras éthoxylés (comme les Simulsol® ox de SEPPIC ou les Rhodasurf® de Solvay), les esters d'acides gras éthoxylés (comme les Atlas® de CRODA), les octylphénols éthoxylés (comme les TRITON® X de Union Carbide), les alkylpolyglucosides ou APG (comme les Simulsol SL® de SEPPIC et Plantacare 2000 UP® de BASF) seuls ou en mélange.  Preferably, the surfactants are chosen from any commercial formulation or any mixture made from chemical families such as ethoxylated or non-ethoxylated sorbitan esters (such as Tween® and Span® from CRODA), ethylene oxide copolymer blocks ( EO) / propylene oxide (OP) (such as Synperonic®PEL from CRODA), alcohols or ethoxylated fatty acids (such as Simulsol® ox from SEPPIC or Solvay's Rhodasurf®), ethoxylated fatty acid esters ( such as CRODA's Atlas®), ethoxylated octylphenols (such as Union Carbide TRITON® X), alkylpolyglucosides or APGs (such as Simulsol SL® from SEPPIC and Plantacare 2000 UP® from BASF) alone or as a mixture.
Selon une autre variante de l'invention, le ou les composés réducteurs ou le ou les précurseurs d'un agent réducteur est de l'urée à 32,5 ± 0,7% massique en solution dans de l'eau déminéralisée ou de l'eau pure, répondant aux spécifications de la norme ISO 22241 According to another variant of the invention, the reducing compound (s) or the precursor (s) of a reducing agent is urea at 32.5 ± 0.7% by weight in solution in demineralised water or pure water, meeting the specifications of ISO 22241
Selon une variante très préférée de la présente invention, la solution contenant le ou les composés réducteurs ou le ou les précurseurs d'un agent réducteur du composé réducteur est préparée à partir d'un produit répondant aux spécifications de la norme ISO 22241, par exemple les produits commerciaux AdBlue®, DEF, AUS32 ou ARLA32. According to a very preferred variant of the present invention, the solution containing the reducing compound (s) or the precursor (s) of a reducing agent of the reducing compound is prepared from a product meeting the specifications of the ISO 22241 standard, for example commercial products AdBlue®, DEF, AUS32 or ARLA32.
Selon une autre variante préférée de la présente invention, la solution contenant le ou les composés réducteurs ou le ou les précurseurs d'un agent réducteur est préparée à partir d'un produit respectant les caractéristiques physiques et chimiques de la norme ISO 22241-1, par exemple le produit commercial Diaxol®.  According to another preferred variant of the present invention, the solution containing the reducing compound (s) or the precursor (s) of a reducing agent is prepared from a product that complies with the physical and chemical characteristics of the ISO 22241-1 standard, for example the commercial product Diaxol®.
Par la suite, le terme Adblue® sera utilisé pour désigner indifféremment les produits suivants : Adblue®, DEF, AUS32, ARLA32 ou Diaxol®. Thereafter, the term Adblue® will be used to refer to the following products: Adblue®, DEF, AUS32, ARLA32 or Diaxol®.
Le fluide pour la dépollution de moteurs thermiques selon l'invention reste préférentiellement stable dans une gamme de température allant de -11 à + 60 °C.  The fluid for the depollution of heat engines according to the invention preferably remains stable in a temperature range of -11 to + 60 ° C.
Enfin le fluide pour la dépollution de moteurs thermiques présente une bonne stabilité vis à vis de la lumière. La présente invention porte également sur différents modes de réalisation du fluide pour la dépollution de moteurs thermiques. Finally, the fluid for the depollution of heat engines has good stability with respect to light. The present invention also relates to different embodiments of the fluid for the depollution of heat engines.
Ainsi selon un premier procédé de réalisation, on additionne un tensioactif dans une solution d'au moins un composé réducteur ou précurseur d'un agent réducteur, puis on additionne la dispersion d'oxydes métalliques qui est mise en émulsion au moyen d'un système approprié de mélange, puis on dilue avec un ajout de solution d'au moins un composé réducteur ou précurseur d'un agent réducteur pour atteindre la teneur en oxydes métalliques désirée.  Thus, according to a first embodiment, a surfactant is added to a solution of at least one reducing compound or precursor of a reducing agent, and then the dispersion of metal oxides which is emulsified by means of a system is added. suitable mixture, and then diluted with a solution addition of at least one reducing compound or precursor of a reducing agent to achieve the desired metal oxide content.
Selon un second procédé de réalisation du fluide pour la dépollution de moteurs thermiques, on additionne un tensioactif dans une solution d'au moins un composé réducteur ou précurseur d'un agent réducteur, puis on additionne la dispersion d'oxydes métalliques qui est mise en émulsion au moyen d'un système approprié de mélange de façon à obtenir directement la teneur en oxydes métalliques désirée. According to a second process for producing the fluid for the depollution of heat engines, a surfactant is added in a solution of at least one reducing compound or precursor of a reducing agent, and then the dispersion of metal oxides is added. emulsion by means of a suitable mixing system so as to obtain directly the desired metal oxide content.
La présente invention porte également sur l'utilisation du fluide de dépollution dans un moteur à combustion interne de type Diesel, l'injection dudit fluide étant réalisée en amont des systèmes de traitement des gaz d'échappement SCR et FAP, (ou de l'unique système de traitement lorsqu'ils sont regroupés en un seul module), et étant opérée de façon régulière en fonction des conditions de fonctionnement du moteur.  The present invention also relates to the use of the depollution fluid in a diesel-type internal combustion engine, the injection of said fluid being carried out upstream of the exhaust gas treatment systems SCR and FAP, (or the single treatment system when grouped into a single module), and being operated regularly according to the operating conditions of the engine.
DESCRIPTION DETAILLEE DE L'INVENTION DETAILED DESCRIPTION OF THE INVENTION
L'invention consiste en un fluide multifonctionnel pour la dépollution des gaz d'échappement provenant d'un moteur à combustion interne. Le fluide multifonctionnel selon l'invention favorise soit la régénération en continu du filtre à particules, soit la combustion des suies lors des phases de régénération actives du FAP, soit permet une combinaison de ces deux avantages. The invention consists of a multifunctional fluid for the depollution of exhaust gases from an internal combustion engine. The multifunctional fluid according to the invention promotes either the continuous regeneration of the particulate filter or the combustion of soot during the active regeneration phases of the FAP, or allows a combination of these two advantages.
Ce fluide se compose essentiellement d'une émulsion entre une dispersion d'un ou plusieurs oxydes métalliques dans un hydrocarbure ou un mélange d'hydrocarbures d'une part, et une solution aqueuse contenant au moins un réducteur ou au moins un précurseur d'agent réducteur des NOx d'autre part. This fluid consists essentially of an emulsion between a dispersion of one or more metal oxides in a hydrocarbon or a mixture of hydrocarbons on the one hand, and an aqueous solution containing at least one reducing agent or at least one agent precursor NOx reducer on the other hand.
Ladite émulsion est rendue possible par la présence d'un ou de plusieurs tensioactifs.  Said emulsion is made possible by the presence of one or more surfactants.
Le fluide ainsi obtenu permet de réaliser concomitamment deux fonctions nécessaires à la dépollution des moteurs thermiques, plus particulièrement de moteur Diesel, la réduction catalytique sélective des NOx et l'aide à l'oxydation des particules piégées dans le FAP par combustion catalytique. The fluid thus obtained makes it possible to concomitantly perform two functions necessary for the depollution of the thermal engines, more particularly of the diesel engine, the reduction catalytic selective NOx and aid in the oxidation of particles trapped in the FAP by catalytic combustion.
La réalisation du fluide selon l'invention conduit à une émulsion qui présente des caractéristiques de stabilité dans le temps, et ce jusqu'à une température de 60 °C.  The production of the fluid according to the invention leads to an emulsion which has stability characteristics over time, up to a temperature of 60.degree.
Le fluide selon l'invention peut être réalisé à partir d'une solution commerciale d'AdBlue® suivant les spécifications ISO 22241. The fluid according to the invention can be made from a commercial solution of AdBlue ® according to ISO 22241 specifications.
Un avantage important du fluide selon l'invention réside dans le fait qu'il cumule les deux fonctions de dépollution des émissions de moteur en un seul fluide.  An important advantage of the fluid according to the invention lies in the fact that it combines the two functions of decontamination of engine emissions in a single fluid.
Un des autres avantages de l'invention est de ne pas modifier sensiblement les propriétés de densité, de viscosité et de conservation de la solution d'AdBlue®, ce qui signifie en pratique qu'aucune modification du système d'injection de l'AdBlue® dans le moteur n'est nécessaire afin de bénéficier des avantages de l'invention. One of the other advantages of the invention is not to substantially modify the density, viscosity and retention properties of the AdBlue ® solution, which means in practice that no modification of the AdBlue injection system ® in the engine is necessary in order to benefit from the advantages of the invention.
Le principe de l'invention est de réunir en un seul fluide d'une part un composé réducteur ou précurseur d'agent réducteur, tel que l'urée, qui va agir comme un agent réducteur, ou comme un précurseur d'agent réducteur comme l'ammoniac, et d'autre part une dispersion d'oxydes métalliques qui, dans la ligne d'échappement sous l'effet de la température et de l'oxygène résiduel des gaz d'échappement, va mettre en contact les suies avec un composé abaissant leur température d'oxydation, ce qui a pour effet d'aider à l'oxydation en continu des suies filtrées et de réduire le coût énergétique d'une régénération active du filtre quand celle-ci est nécessaire. Un autre effet des oxydes métalliques est d'accroître la vitesse d'oxydation des suies par un processus catalytique et donc de régénérer le FAP en une durée réduite.  The principle of the invention is to combine in a single fluid on the one hand a reducing agent or reducing agent precursor, such as urea, which will act as a reducing agent, or as a reducing agent precursor such as ammonia, and secondly a dispersion of metal oxides which, in the exhaust line under the effect of the temperature and the residual oxygen of the exhaust gas, will put soot in contact with a the compound lowers their oxidation temperature, which has the effect of aiding in the continuous oxidation of the filtered soot and reducing the energy cost of active regeneration of the filter when it is necessary. Another effect of the metal oxides is to increase the rate of oxidation of soot by a catalytic process and thus regenerate the FAP in a reduced time.
Il existe différentes manières de réaliser le fluide selon l'invention correspondant à plusieurs variantes. There are different ways of producing the fluid according to the invention corresponding to several variants.
La plus simple consiste à modifier une solution commerciale d'AdBlue® ou à réaliser une solution d'urée suivant les spécifications ISO 22241, ou bien encore, utiliser un autre composé réducteur tel que l'ammoniac par exemple. The simplest is to modify a commercial solution of AdBlue ® or to make a solution of urea according to ISO 22241 specifications, or even to use another reducing compound such as ammonia for example.
Il est possible de réaliser des émulsions stables avec différents tensioactifs non ioniques et dispersions susceptibles d'apporter une concentration suffisante d'au moins un oxyde métallique favorisant l'oxydation des suies. La suite de la description détaille plusieurs modes de réalisation du fluide selon l'invention. La chimie des tensioactifs est très riche et trouve de nombreuses applications dans des domaines aussi variés que l'industrie cosmétique, pharmaceutique, routière, et de la détergence par exemple. It is possible to produce stable emulsions with different nonionic surfactants and dispersions capable of providing a sufficient concentration of at least one metal oxide promoting the oxidation of soot. The remainder of the description details several embodiments of the fluid according to the invention. The chemistry of surfactants is very rich and has many applications in fields as varied as the cosmetic, pharmaceutical, road and detergency industry, for example.
Les tensioactifs sont nombreux. Ils peuvent être dissociés en tensioactifs cationiques, anioniques et non ioniques.  Surfactants are numerous. They can be dissociated into cationic, anionic and nonionic surfactants.
L'émulsification (c'est-à-dire le processus de dispersion d'huile dans eau) peut être réalisée par tout moyen approprié à l'aide de tout mélangeur dynamique en batch ou en continu connu de l'homme de l'art.  The emulsification (that is to say the process of dispersion of oil in water) can be carried out by any appropriate means using any batch dynamic mixer or continuous known to those skilled in the art .
Des dispositifs de ce genre sont par exemple des mélangeurs à rotor et stator (par exemple ceux commercialisés par la société VMI Rayneri sous la marque Ultramix®), des moulins colloïdaux, des homogénéisateurs haute pression ou encore des dispositifs à ultrasons.  Devices of this type are, for example, rotor and stator mixers (for example those marketed by Rayneri under the brand name Ultramix®), colloid mills, high-pressure homogenizers or ultrasound devices.
Conviennent particulièrement les dispositifs constitués d'un agitateur rotatif comprenant un ou plusieurs mobiles fixés sur un arbre, qui dissipent des puissances volumiques de l'ordre de 103 à 109 W/m3. Particularly suitable are devices consisting of a rotary agitator comprising one or more mobiles fixed on a shaft, which dissipate power densities of the order of 10 3 to 10 9 W / m 3 .
La teneur en oxydes métalliques dans la composition finale du fluide selon l'invention peut être comprise entre 1 et 10000 ppm, de préférence entre 1 et 5000 ppm, et d'une manière encore préférée entre 10 et 2000 ppm. The content of metal oxides in the final composition of the fluid according to the invention may be between 1 and 10,000 ppm, preferably between 1 and 5000 ppm, and more preferably between 10 and 2000 ppm.
La réduction de la teneur en métal permet de limiter l'accumulation de cendres métalliques dans le FAP.  The reduction of the metal content makes it possible to limit the accumulation of metallic ash in the FAP.
Le fluide tel que décrit dans la présente invention est stable dans le temps. L'action de la lumière ne modifie pas la stabilité de l'émulsion, et les conditions de cristallisation et de stabilité de l'urée ne sont pas affectées. The fluid as described in the present invention is stable over time. The action of light does not alter the stability of the emulsion, and the conditions of crystallization and stability of urea are not affected.
L'exposition prolongée à des températures de +60 °C n'altère pas non plus cette stabilité. Prolonged exposure to temperatures of +60 ° C does not alter this stability either.
Le dégel de la solution après gel à cœur permet de retrouver les propriétés de la solution avant gel (pas de décantation ou coalescence). Enfin, dans le cas où le fluide est préparé à partir d'une solution d'urée ou d'AdBlue®, la quantité des agents additionnés à la solution reste faible et permet de satisfaire à la concentration d'urée normalisée de 32,5 ± 0,7 %. The thawing of the solution after core gel makes it possible to recover the properties of the solution before freezing (no settling or coalescence). Finally, in the case where the fluid is prepared from a solution of urea or AdBlue ® , the amount of agents added to the solution remains low and allows to meet the standardized urea concentration of 32.5. ± 0.7%.
Le caractère inventif de l'invention réside dans la sélection judicieuse des composants de la formulation. Il n'est pas évident de réaliser une émulsion stable entre d'une part une dispersion d'oxydes métalliques dans un ou des hydrocarbures, et d'autre part une solution aqueuse d'urée. En effet, naturellement, ces deux phases, l'une aqueuse, l'autre huileuse, ne sont pas miscibles. EXEMPLES SELON L'INVENTION The inventive nature of the invention lies in the judicious selection of the components of the formulation. It is not easy to produce a stable emulsion between, on the one hand, a dispersion of metal oxides in one or more hydrocarbons, and, on the other hand, an aqueous solution of urea. Indeed, of course, these two phases, one aqueous, the other oily, are immiscible. EXAMPLES ACCORDING TO THE INVENTION
Les exemples qui suivent décrivent quatre modes de préparation du fluide selon l'invention. Ces exemples ne sont pas limitatifs des possibilités de l'invention, mais sont donnés à titre illustratif.  The examples which follow describe four modes of preparation of the fluid according to the invention. These examples are not limiting of the possibilities of the invention, but are given for illustrative purposes.
Le fluide peut être préparé à température ambiante ou à une température inférieure à 60 °C. Lorsque le fluide présente deux phases distinctes, il ne répond pas aux spécifications. The fluid can be prepared at room temperature or at a temperature below 60 ° C. When the fluid has two distinct phases, it does not meet the specifications.
Ces quelques cas de figure démontrent que l'obtention d'un fluide selon l'invention n'a pas de caractère systématique. Tous les exemples décrits ont été réalisés avec une solution d'AdBlue® commercial pour la solution d'urée, et avec de l'Eolys Powerflex® commercial pour la dispersion d'oxydes métalliques dans des hydrocarbures. These few cases show that obtaining a fluid according to the invention is not systematic. All the examples described were performed with a solution of AdBlue ® trade to the urea solution, and with Eolys Powerflex trade ® for dispersing metal oxides in hydrocarbons.
Exemples suivant le procédé de réalisation 1 Examples according to the production method 1
Le fluide est réalisé comme suit : dans un flacon en verre de 150 cm , on introduit 51 g d'AdBlue®, on additionne une masse de tensioactif de 1,5 grammes qu'on disperse à l'aide d'un agitateur manuel. On introduit ensuite 3 g d' Eolys Powerflex® qu'on disperse à l'aide d'un mélangeur de laboratoire muni d'une pale adaptée à la formation d'une émulsion. Après 5 minutes d'agitation à température ambiante, on évalue l'aspect du fluide. The fluid is produced as follows: 51 g of AdBlue ® are introduced into a 150 cm glass flask, a mass of surfactant of 1.5 grams is added and dispersed by means of a manual stirrer. Then introduced 3 g of Eolys Powerflex ® is dispersed using a laboratory mixer provided with a blade adapted to the formation of an emulsion. After stirring for 5 minutes at room temperature, the appearance of the fluid is evaluated.
Tableau 1 : procédé de réalisation 1 Table 1: Production method 1
On vérifie qu'il existe des compositions du fluide donnant des émulsions d'apparence homogène, sans dépôt de solide, qu'on dilue ensuite avec la quantité nécessaire d'AdBlue® pour atteindre la concentration en oxydes métalliques cible comprise dans l'exemple entre 300 et 400 ppm. A nouveau, on évalue l'aspect du fluide. On vérifie que les compositions du fluide restent des émulsions d'apparence homogène, sans dépôt de solide ou de séparation de phases. Dans le tableau 1, les exemples 1 et 3 ne satisfont pas à l'invention, car ils conduisent à un fluide hétérogène. L'exemple 2 satisfait aux critères de l'invention. It is verified that there are fluid compositions providing emulsions of uniform appearance without solid deposit, which is then diluted with the required amount of AdBlue ® to achieve the target metal oxide concentration in the example between 300 and 400 ppm. Again, the appearance of the fluid is evaluated. It is verified that the compositions of the fluid remain emulsions of homogeneous appearance, without solid deposition or phase separation. In Table 1, Examples 1 and 3 do not satisfy the invention because they lead to a heterogeneous fluid. Example 2 satisfies the criteria of the invention.
Exemples suivant le procédé de réalisation 2 Examples according to the embodiment method 2
Le fluide est réalisé comme suit : dans un flacon en verre de 250 cm , on introduit 100 g d'AdBlue®, on additionne une masse de tensioactif de 1 gramme qu'on disperse à l'aide d'un agitateur manuel. On introduit ensuite 2 g d' Eolys Powerflex® qu'on disperse à l'aide d'un mélangeur de laboratoire muni d'une pale adaptée à la formation d'une émulsion. Après 15 minutes d'agitation à température ambiante, on évalue l'aspect du fluide obtenu. The fluid is produced as follows: 100 g of AdBlue ® are added to a 250 cm glass flask and a mass of 1 gram surfactant is added and dispersed by means of a manual stirrer. Then added 2 g of Eolys Powerflex ® is dispersed using a laboratory mixer provided with a blade adapted to the formation of an emulsion. After stirring for 15 minutes at room temperature, the appearance of the fluid obtained is evaluated.
Tableau 2 : procédé de réalisation 2 Table 2: Production Method 2
On vérifie qu'il existe des compositions de fluide donnant des émulsions d'apparence homogène, sans dépôt de solide. It is verified that there are fluid compositions giving emulsions of homogeneous appearance, without deposition of solid.
Dans le tableau 2, les exemples 4 et 6 ne satisfont pas à l'invention, car ils conduisent à un fluide hétérogène. L'exemple 5 satisfait aux critères de l'invention.  In Table 2, Examples 4 and 6 do not satisfy the invention because they lead to a heterogeneous fluid. Example 5 satisfies the criteria of the invention.
Exemples illustrant la stabilité du fluide en fonction de la température Examples illustrating fluid stability as a function of temperature
Afin de vérifier que les exemples de fluide suivant l'invention ne modifient pas la température de cristallisation, nous plaçons pendant deux heures des tubes à essai contenant les compositions du fluide suivant l'invention dans un bac froid maintenu à - 10 ± 1 °C. Nous constatons qu'à cette température le fluide reste d'aspect homogène. Exemple Exemple testé Aspect du fluide à -10 °C In order to verify that the examples of fluid according to the invention do not modify the crystallization temperature, we place for two hours test tubes containing the compositions of the fluid according to the invention in a cold tank maintained at -10 ± 1 ° C. . We find that at this temperature the fluid remains homogeneous. Example Example tested Aspect of the fluid at -10 ° C
7 Exemple 2 Aspect homogène, liquide  7 Example 2 Homogeneous appearance, liquid
8 Exemple 5 Aspect homogène, liquide  Example 5 Homogeneous appearance, liquid
Tableau 3 : Evaluation des caractéristiques de différents fluides selon l'invention à une température proche de celle de cristallisation de l'AdBlue Afin de vérifier que les exemples de fluide suivant l'invention restent stables après cristallisation due au froid puis dégel, nous plaçons pendant deux heures des tubes à essai contenant les différents fluides suivant l'invention dans un bac froid maintenu à - 18 ± 1 °C, puis nous les en retirons après avoir constaté l'état solidifié des fluides pour les replacer à température ambiante pendant deux heures. Nous constatons que les différents fluides ont repris leur aspect homogène, liquide. Table 3: Evaluation of the characteristics of different fluids according to the invention at a temperature close to that of crystallization of AdBlue In order to verify that the examples of the fluid according to the invention remain stable after crystallization due to the cold then thaw, we place during two hours of the test tubes containing the various fluids according to the invention in a cold tank maintained at -18 ± 1 ° C, and then we remove them after having noted the solidified state of the fluids to replace them at room temperature for two hours . We note that the different fluids have returned to their homogeneous, liquid appearance.
Tableau 4 : Influence du gel/dégel sur la stabilité de différents fluides selon l'invention Table 4: Influence of freeze / thaw on the stability of different fluids according to the invention

Claims

REVENDICATIONS
1) Fluide pour la dépollution de moteurs thermiques, notamment Diesel, permettant d'effectuer à la fois la réduction catalytique sélective des oxydes d'azote contenus dans les gaz d'échappement, ainsi que l'aide à la régénération du filtre à particules (FAP) par combustion catalytique des particules de suies déposées dans le filtre à particules, ce fluide étant constitué d'une émulsion comprenant : 1) Fluid for the depollution of thermal engines, in particular Diesel, which makes it possible to carry out both the selective catalytic reduction of the nitrogen oxides contained in the exhaust gases, as well as the aid for the regeneration of the particulate filter ( FAP) by catalytic combustion of soot particles deposited in the particulate filter, this fluid consisting of an emulsion comprising:
- une solution aqueuse d'au moins un composé réducteur ou précurseur d'un agent réducteur,  an aqueous solution of at least one reducing compound or precursor of a reducing agent,
- une dispersion d'oxydes métalliques dans un hydrocarbure ou un mélange d'hydrocarbures,  a dispersion of metal oxides in a hydrocarbon or a mixture of hydrocarbons,
- un tensioactif ou d'un mélange de tensioactifs permettant la fabrication et la stabilisation d'une émulsion stable du type huile dans eau.  - A surfactant or a mixture of surfactants for the manufacture and stabilization of a stable emulsion of oil-in-water type.
2) Fluide pour la dépollution de moteurs thermiques, notamment Diesel, selon la revendication 1, dans lequel les ions métalliques pris seuls ou en combinaison sont choisis dans la liste de métaux suivants: Fe, Cu, Ni, Co, Zn, Mn, Ti, V, Sr, Pt, Ce, Ca,2) Fluid for the depollution of heat engines, especially diesel, according to claim 1, wherein the metal ions taken alone or in combination are selected from the following list of metals: Fe, Cu, Ni, Co, Zn, Mn, Ti , V, Sr, Pt, Ce, Ca,
Li, Na, Nb, et préférentiellement dans la liste suivante Fe, Ce, Cu, Sr. Li, Na, Nb, and preferentially in the following list Fe, Ce, Cu, Sr.
3) Fluide pour la dépollution de moteurs thermiques notamment Diesel, selon l'une des revendications de 1 à 2, dans lequel la dispersion d'oxydes métalliques se présente sous forme de dispersion d'oxyde de fer ou de mélange d'oxydes de fer dans un mélange d'hydrocarbures de type Eolys Powerflex®. 3) Fluid for the depollution of heat engines including diesel, according to one of claims 1 to 2, wherein the dispersion of metal oxides is in the form of dispersion of iron oxide or iron oxide mixture in a mixture of Eolys Powerflex® type hydrocarbons.
4) Fluide pour la dépollution de moteurs thermiques, notamment Diesel selon l'une des revendications 1 à 3, dans lequel le composé réducteur ou précurseur d'un agent réducteur en solution aqueuse est sélectionné parmi l'urée, l'ammoniaque, le formamide, et les sels d'ammonium, notamment le formiate d'ammonium, le carbamate d'ammonium, les sels de guanidine, notamment le formiate de guanidinium. 4) Fluid for the depollution of heat engines, especially diesel according to one of claims 1 to 3, wherein the reducing compound or precursor of a reducing agent in aqueous solution is selected from urea, ammonia, formamide and ammonium salts, especially ammonium formate, ammonium carbamate, guanidine salts, especially guanidinium formate.
5) Fluide pour la dépollution de moteurs thermiques, notamment Diesel, selon l'une des revendication 1 à 4, dans lequel la concentration en ion métallique dans émulsion réalisée au moyen du ou des tensioactifs avec le composé réducteur ou précurseur d'un agent réducteur, est comprise entre 10 et 10000 ppm, de préférence entre 10 et 5000 ppm, et d'une manière préférée entre 10 et 2000 ppm. 5) Fluid for the depollution of heat engines, particularly diesel, according to one of claims 1 to 4, wherein the concentration of metal ion in emulsion carried out with the surfactant or surfactants with the reducing compound or precursor of a reducing agent is between 10 and 10000 ppm, preferably between 10 and 5000 ppm, and preferably between 10 and 2000 ppm.
6) Fluide pour la dépollution de moteurs thermiques, notamment Diesel, selon l'une des revendications 1 à 5, dans lequel le tensioactif est anionique, cationique ou non ionique. 7) Fluide pour la dépollution de moteurs thermiques, selon la revendication 6, dans lequel le tensioactif est non ionique. 6) Fluid for the depollution of heat engines, especially diesel, according to one of claims 1 to 5, wherein the surfactant is anionic, cationic or nonionic. 7) fluid for the depollution of thermal engines, according to claim 6, wherein the surfactant is nonionic.
8) Fluide pour la dépollution de moteurs thermiques, selon la revendication 7, dans lequel le tensioactif est soluble dans l'eau et a une HLB (balance hydrophile/lipophile) comprise entre 7 et 16. 8) fluid for the depollution of thermal engines, according to claim 7, wherein the surfactant is soluble in water and has a HLB (hydrophilic balance / lipophilic) of between 7 and 16.
9) Fluide pour la dépollution de moteurs thermiques, selon la revendication 8, dans lequel tensioactif est choisi parmi tout mélange fabriqué à partir de familles chimiques telles que les esters de sorbitan éthoxylés ou non (comme les Tween® et Span® de CRODA), les blocs copolymères oxyde d'éthylène (OE)/oxyde de propylène (OP) (comme les Synperonic®PEL de CRODA), les alcools ou les acides gras éthoxylés (comme les9) A fluid for the depollution of thermal engines, according to claim 8, wherein the surfactant is chosen from any mixture made from chemical families such as ethoxylated or non-ethoxylated sorbitan esters (such as Tween® and Span® from CRODA), ethylene oxide (EO) / propylene oxide (OP) copolymer blocks (such as Synperonic®PEL from Croda), alcohols or ethoxylated fatty acids (such as
Simulsol® ox de SEPPIC ou les Rhodasurf® de Solvay), les esters d'acides gras éthoxylés (comme les Atlas® de CRODA), les octylphénols éthoxylés (comme les TRITON® X de Union Carbide), les alkylpolyglucosides ou APG (comme les Simulsol SL® de SEPPIC et Plantacare 2000 UP® de BASF) seuls ou en mélange. 10) Fluide pour la dépollution de moteurs thermiques, selon l'une des revendications 1 à 9, dans lequel le composé réducteur ou précurseur d'un agent réducteur est de l'urée à 32,5 ± 0,7 % massique en solution dans de l'eau déminéralisée répondant aux spécifications de là norme ISO 22241. Simulsol® ox from SEPPIC or Solvay's Rhodasurf®), ethoxylated fatty acid esters (such as Atlas® from CRODA), ethoxylated octylphenols (such as Union Carbide TRITON® X), alkylpolyglucosides or APG (such as Simulsol SL® from SEPPIC and Plantacare 2000 UP® from BASF) alone or as a mixture. 10) Fluid for the depollution of heat engines, according to one of claims 1 to 9, wherein the reducing compound or precursor of a reducing agent is urea 32.5 ± 0.7 mass% in solution in Demineralized water meeting the specifications of ISO 22241.
11) Fluide pour la dépollution de moteurs thermiques selon l'une quelconque des revendications 1 à 10, dans lequel la solution du composé réducteur est préparée à partir du produit commercial AdBlue®. 11) Heat engine depollution fluid according to any one of claims 1 to 10, wherein the solution of the reducing compound is prepared from the commercial product AdBlue ® .
12) Fluide pour la dépollution de moteurs thermiques selon l'une quelconque des revendications 1 à 11, dans lequel le fluide reste stable dans une gamme de température allant de -11 à + 60°C. 13) Procédé de préparation du fluide pour la dépollution de moteurs thermiques selon les revendications 1 à 12, selon lequel on additionne un tensioactif dans une solution aqueuse d'au moins un composé réducteur ou précurseur d'un agent réducteur, puis on additionne la dispersion d'oxydes métalliques qui est mise en émulsion au moyen d'un système approprié de mélange, puis on dilue avec un ajout de solution aqueuse d'au moins un composé réducteur ou précurseur d'un agent réducteur pour atteindre la teneur en oxydes métalliques désirée. 14) Utilisation du fluide pour la dépollution de moteurs thermiques selon l'une des revendications 1 à 12 dans un moteur à combustion interne de type Diesel, l'injection dudit fluide étant réalisée en amont des système de traitement des gaz d'échappement SCR et FAP, et étant opérée de façon régulière en fonction des conditions de fonctionnement du moteur. 12) Fluid for the depollution of heat engines according to any one of claims 1 to 11, wherein the fluid remains stable in a temperature range of -11 to + 60 ° C. 13) Process for the preparation of the fluid for the depollution of heat engines according to claims 1 to 12, wherein a surfactant is added in an aqueous solution of at least one reducing compound or precursor of a reducing agent, and then adding the dispersion of metal oxides which is emulsified by means of a suitable mixing system, and then diluted with an addition of aqueous solution of at least one reducing compound or precursor of a reducing agent to achieve the desired metal oxide content . 14) Use of the fluid for the depollution of heat engines according to one of claims 1 to 12 in a diesel-type internal combustion engine, the injection of said fluid being performed upstream of the exhaust gas treatment system SCR and FAP, and being operated regularly according to the operating conditions of the engine.
EP16784197.2A 2015-11-13 2016-10-20 Fluid for purifying heat engines and methods for preparing said fluids by emulsification Withdrawn EP3374062A1 (en)

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FR1560908A FR3043570B1 (en) 2015-11-13 2015-11-13 FLUID FOR DEPOLLUTION OF THERMAL ENGINES AND METHODS OF PREPARATION OF SUCH FLUIDS BY EMULSIFICATION
PCT/EP2016/075196 WO2017080777A1 (en) 2015-11-13 2016-10-20 Fluid for purifying heat engines and methods for preparing said fluids by emulsification

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FR3059566B1 (en) 2016-12-07 2022-04-22 Ifp Energies Now EXHAUST GAS DEPOLLUTION FLUID COMPRISING A SOLUBLE BASIC METALLIC CARBONATE, METHOD FOR PREPARING IT AND ITS USE FOR INTERNAL COMBUSTION ENGINES
FR3108529A1 (en) * 2020-03-30 2021-10-01 Total Marketing Services Use of a composition comprising a reducing agent, at least one paraffin and a metal compound to prevent deposits in the exhaust lines comprising an SCR catalyst
FR3138048A1 (en) * 2022-07-19 2024-01-26 Totalenergies Onetech Aqueous composition for exhaust gas treatment with improved properties

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1462228A (en) 1965-07-08 1966-04-15 Saint Gobain Process for obtaining foams of phenolic resins
DE10022763A1 (en) * 2000-05-10 2001-11-22 Siemens Ag Catalytically converting nitrogen oxide in exhaust gas stream mixed with ammonia to form water and nitrogen comprises feeding gas stream together with added catalytically active substance to reaction chamber
US5283001A (en) * 1986-11-24 1994-02-01 Canadian Occidental Petroleum Ltd. Process for preparing a water continuous emulsion from heavy crude fraction
US5874294A (en) * 1990-11-21 1999-02-23 Valentine; James M. Biodesulfurization of fuels
US6003303A (en) * 1993-01-11 1999-12-21 Clean Diesel Technologies, Inc. Methods for reducing harmful emissions from a diesel engine
US5404841A (en) * 1993-08-30 1995-04-11 Valentine; James M. Reduction of nitrogen oxides emissions from diesel engines
US20050002902A1 (en) * 1995-12-28 2005-01-06 Liming Yu Hybrid with interferon-alpha and an immunoglobulin Fc for treatment of tumors and viral infections
US5809774A (en) * 1996-11-19 1998-09-22 Clean Diesel Technologies, Inc. System for fueling and feeding chemicals to internal combustion engines for NOx reduction
AU1578100A (en) * 1999-11-17 2001-05-30 Andras Bertha Fuel oils providing exhaust gases with low NOx contents when combusted
GB9927563D0 (en) * 1999-11-23 2000-01-19 Williamson Ian A process and method for blending a fuel containing a high molecular weight compound
FR2833862B1 (en) 2001-12-21 2004-10-15 Rhodia Elect & Catalysis ORGANIC COLLOIDAL DISPERSION OF IRON PARTICLES, PROCESS FOR PREPARING THE SAME, AND ITS USE AS A FUEL ADJUVANT FOR INTERNAL COMBUSTION ENGINES
EP1344812A1 (en) * 2002-03-13 2003-09-17 Infineum International Limited Overbased metallic salt diesel fuel additive compositions for improvement of particulate traps
US7435707B2 (en) * 2002-05-23 2008-10-14 The Lubrizol Corporation Oil-in-water emulsions and a method of producing
US20030226312A1 (en) * 2002-06-07 2003-12-11 Roos Joseph W. Aqueous additives in hydrocarbonaceous fuel combustion systems
US20040111955A1 (en) * 2002-12-13 2004-06-17 Mullay John J. Emulsified water blended fuels produced by using a low energy process and novel surfuctant
DE10330741A1 (en) * 2003-07-07 2005-01-27 Daimlerchrysler Ag Display device and method for driving a display device for motor vehicles
US8206470B1 (en) * 2005-08-03 2012-06-26 Jacobson William O Combustion emission-reducing method
JP5659165B2 (en) * 2008-12-24 2015-01-28 ビーエーエスエフ コーポレーション Emission treatment system and method using catalytic SCR filter and downstream SCR catalyst
KR101448734B1 (en) * 2009-03-09 2014-10-08 현대자동차 주식회사 Nox reduction catalyst and exhaust system using the same
FR2947004B1 (en) 2009-06-22 2015-12-11 Faurecia Sys Echappement EXHAUST LINE WITH DEVICE FOR TREATING NITROGEN OXIDES.
CA2802516A1 (en) * 2010-06-15 2011-12-22 The Lubrizol Corporation Methods of removing deposits in oil and gas applications
DE102010025880A1 (en) * 2010-07-02 2012-01-05 Emitec Gesellschaft Für Emissionstechnologie Mbh Exhaust treatment device
US20110165040A1 (en) * 2010-11-03 2011-07-07 Ford Global Technologies, Llc Device for remediating emissions and method of manufacture
FR2969653B1 (en) 2010-12-22 2013-02-08 Rhodia Operations ORGANIC DISPERSION OF IRON-BASED PARTICLES IN CRYSTALLIZED FORM
EP2568137B1 (en) * 2011-09-08 2015-08-05 Ford Global Technologies, LLC Heated injection system for exhaust gas systems of Diesel engines
US9957454B2 (en) * 2012-08-10 2018-05-01 ADA-ES, Inc. Method and additive for controlling nitrogen oxide emissions
US8999277B2 (en) * 2013-06-17 2015-04-07 Deere & Company Diesel exhaust fluid formulation that reduces urea deposits in exhaust systems
US9194268B2 (en) * 2013-10-14 2015-11-24 GM Global Technology Operations LLC Exhaust gas treatment system including an enhanced SCR diagnostic unit

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US20180371974A1 (en) 2018-12-27
FR3043570A1 (en) 2017-05-19
US10774709B2 (en) 2020-09-15

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