Patent Application
20140007495
The present invention relates to the use of organic dispersions (organosols) as a fuel additive for internal combustion engines.
During combustion of fuel and notably of gas oil in a diesel engine, the carbonaceous products tend to form carbonaceous particles, which will be designated in the following of the description under the expression of “soots”, which are said to be noxious both for the environment and for health. For a long time, there has been a search for techniques with which the emission of these soots may be reduced.
A satisfactory solution consists of introducing into the exhaust line a particle filter (or PF in the following of the text) which will block soots in its channels in order to discharge a gas without any soots. When a certain amount of accumulated soots in the PF is attained, the soots are burned in order to free the channels of the PF. This step for regenerating the PF is usually accomplished at greater temperatures than the temperature of the gas during normal operation of the engine, the soots usually burning in air at temperatures above 650° C.
In order to assist with regeneration of the PF, a catalyst is generally used which has the purpose of facilitating oxidation of the soots either directly or indirectly. By facilitating the oxidation of the soots is meant the fact of allowing their oxidation at a lower temperature so that this temperature is attained more frequently during normal operation of the engine. A portion of the soots may thus be continuously burned during the operation of the engine.
The catalyst also gives the possibility of lowering the temperature required for regenerating the PF so that the regeneration temperature is less than the combustion temperature of the soots in the absence of said catalyst. The catalyst also allows acceleration of the oxidation rate of the soots which allows a reduction in the required time for regenerating the PF.
The use of an additive for assisting with regeneration of the PF, vectorized by the fuel feeding the engine or further a fuel borne catalyst (FBC) proved to meet many criteria since it allows regeneration of the PF more rapidly and at a lower temperature than the competing technology called catalyzed soot filter (CSF, the catalyst being immobilized in the PF), which contributes to reducing fuel consumption for regenerating the PF (and thus reducing CO2 emissions).
Among additives for assisting with regeneration of the PF, dispersions of rare earths, notably based on cerium are known for being efficient for regenerating the PF and contribute to the reduction in the oxidation temperature.
Dispersions of iron compounds used as an additive of fuels may contribute to the reduction of this self-ignition temperature of the soots.
The presence of an FBC in the fuel may sometimes lead to reducing the resistance of the fuel to oxidation, notably when it contains biofuels.
It is thus sought to obtain dispersions having good dispersibility, high stability over time and further improved compatibility in the medium into which they are introduced, notably an improved resistance to oxidation, particularly in the presence of biofuels.
It is preferably sought to obtain dispersions having sufficient catalytic activity at a relatively not very high concentration.
One of the objects of the present invention is to allow regeneration of PFs by means of a fuel additive.
With this purpose, the invention proposes the use of colloidal dispersions comprising particles, most of them not being aggregated with each other and having good monodispersity as a fuel additive.
More specifically, the invention relates to the use of a dispersion comprising:
The invention also relates to a method for preparing a fuel additive according to the invention, comprising a step for putting into contact and mixing a fuel and a dispersion according to the invention, whereby the additived fuel is obtained.
The solid objects dispersed in the dispersions of the invention are individualized solid particles or aggregates of such particles. Said particles may further optionally contain residual amounts of bound or adsorbed ions such as for example sodium ions or ammonium ions.
The dispersion of the invention has the advantage of being very stable. The particles of the dispersion of the invention do not settle, and the dispersions do not decant, even after several months. Further, it may have good compatibility with fuels of the gas oil type notably based on biofuels.
According to a preferred alternative, it may further have high catalytic activity.
The dispersion of the invention is a dispersion in an organic phase.
This organic phase is notably selected depending on the use of the dispersion.
According to a first embodiment, the organic phase comprises an apolar solvent, preferably selected from apolar hydrocarbons or mixtures thereof.
By <<apolar solvent>>, is meant a solvent having very little affinity for water and relatively low miscibility in water. Generally, an apolar solvent is a solvent for which the resulting dipolar moment is zero. This may therefore be a molecule not including any polar group (such as for example cyclohexane) or a molecule including polar groups but the geometry of which ensures that the dipolar moment is cancelled (such as for example carbon tetrachloride).
For this purpose, most often, the organic phase consists of at least 80%, preferably at least 90%, preferably at least 95% by mass of an apolar solvent or of a mixture of apolar solvents, based on the total mass of the organic phase.
According to this embodiment, the organic phase generally comprises at least 70%, preferably at least 80%, preferentially at least 90%, advantageously at least 95% by mass of an apolar hydrocarbon or of a mixture of apolar hydrocarbons.
The organic phase typically only consists of an apolar hydrocarbon or of a mixture of apolar hydrocarbons.
As an example of an apolar solvent, mention may be made of aliphatic hydrocarbons such as hexane, heptane, octane, nonane, cycloaliphatic hydrocarbons such as cyclohexane, cyclopentane, cycloheptane. Petroleum cuts of the Isopar type, essentially containing isoparaffinic and paraffinic C-11 and C-12 hydrocarbons are also suitable.
It is also possible to apply as an apolar solvent, apolar chlorinated hydrocarbons.
According to a second embodiment, the organic phase comprises a polar solvent, preferably selected from polar hydrocarbons or mixtures thereof.
By <<polar solvent>>, is notably meant a solvent having a non-zero resulting dipolar moment. This may therefore be a molecule including one or several polar groups.
According to this embodiment, the organic phase generally comprises at least 70%, preferably at least 80%, preferentially at least 90%, advantageously less than 95% by mass of a polar hydrocarbon or of a mixture of polar hydrocarbons.
The organic phase typically only consists of a polar hydrocarbon all of a mixture of polar hydrocarbons.
By <<polar solvent>>, are more generally meant solvents which have group affinity towards water and good miscibility in water.
As an example of a polar solvent, mention may be made or aromatic hydrocarbons such as benzene, toluene, ethyl benzene, xylenes, liquid naphthenes. Petroleum cuts of the Solvesso type (a trademark by EXXON), notably Solvesso 100 which essentially contains a mixture of methyl ethyl and trimethyl benzene and Solvesso 150 which contains a mixture of alkylbenzenes, in particular dimethyl benzene and tetraethyl benzene, are also suitable.
It is also possible to apply for the organic phase, polar chlorinated hydrocarbons such as chloro- or dichloro-benzene, chlorotoluene. Ethers as well as aliphatic and cycloaliphatic ketones such as for example diisopropyl ether, dibutyl ether, methylisobutylketone, diisobutylketone, mesityl oxide, may be contemplated.
It is also possible to contemplate polar solvents based on alcohol such as 2-ethylhexanol.
According to an alternative, the organic phase comprises a mixture of an apolar solvent and of a polar solvent as described above.
The dispersion according to the invention includes at least one amphiphilic agent.
This amphiphilic agent has the effect of stabilizing the dispersion of particles. It is also used as a phase transfer agent during the preparation of the dispersions (between the aqueous phase and the organic phase).
Preferably, the amphiphilic agent is a carboxylic acid which generally includes from 10 to 50 carbon atoms, preferably from 10 to 25 carbon atoms.
This acid may be linear or branched. It may be selected from aryl, aliphatic or arylaliphatic acids optionally bearing other functions provided that these functions are stable in the media which are desirably used for the dispersions according to the present invention.
Thus, it is possible to apply for example aliphatic carboxylic acids which are natural or synthetic. Of course, it is possible to use acids in a mixture.
As an example, mention may be made of tallol, soya bean oil, tallow oil, flax oil, fatty acids, oleic acid, linoleic acid, stearic acid and its isomers, pelargonic acid, capric acid, lauric acid, myristic acid, dodecylbenzenesulfonic acid, ethyl-2-hexanoic acid, naphthenic acid, hexoic acid.
As a preferred amphiphlic agent, mention may be made of stearic acid and of its isomers such as for example a mixture of acids or products which contain chain length distributions such as Prisorine 3501 of Croda.
This amphiphilic agent may also be composed of one or several polyacids such as succinic acids substituted with polybutenyl groups. These polyacids may be used alone or in a combination with one or several aliphatic monocarboxylic acids containing between 10 and 20 carbon atoms on average.
As an example, mention may be made of the mixture of oleic acid with one or several succinic acids substituted with polybutenyl groups, in which the polybutenyl groups have an average molecular weight (as measured by gas chromatography) comprised between 500 and 1,300 and more particularly between 700 and 1,000 g·mol−1.
According to a feature of the invention, the particles of the dispersion of the invention are based on an iron compound in crystallized form.
This crystallized form which may be obtained by applying the steps of the method which will be described further on, may notably be observed by the X-ray diffraction technique (XRD) which shows characteristic peaks of at least one defined crystallized structure of iron.
The solid objects of the dispersion of the invention are in the form or particles, or aggregates of particles, of an iron compound, the composition of which essentially corresponds to an iron oxide in crystallized form.
The crystallized forms of iron oxide making up the particles according to the invention are typically Fe(III) oxides of the maghemite (γ-Fe2O3) type and/or Fe(II) and Fe(III) oxides of the magnetite (Fe3O4) type.
The aforementioned method generally gives the possibility of obtaining particles based on Fe(III) oxide of the maghemite type and/or Fe(II) and Fe(III) oxide of the magnetite type, the magnetite may then be oxidized into Fe(III) oxide of the maghemite type, for example upon contact with oxygen.
Preferably, the particles with a size greater than or equal to 4 nm in the dispersion are, for at least 90% of them, in the form of an iron compound in crystallized form, advantageously at least 95%, preferentially at least 99%.
According to another feature of the invention, the average size D. as measured by XRD of the particles of the dispersion is less than or equal to 7 nm, preferably less than or equal to 6 nm, preferentially less than or equal to 5 nm.
Generally this size is of at least 4 nm.
The crystallized nature of the particles according to the invention may notably be shown by XRD analysis. The XRD diagram allows definition of two features of these particles:
The XRD analysis may for example be carried out on a commercial apparatus of the X'Pert PRO MPD PANalytical type notably composed of a θ-θ, allowing characterization of liquid samples. The sample remains horizontal during acquisition and the source and the detector are the ones which move.
This installation is driven by the software package X'Pert Datacollector provided by the supplier and exploitation of the obtained diffraction diagram may be carried out by means of the software package X'Pert HighScore Plus version 2.0 or more (supplier PANalytical).
According to another feature of the invention, it is preferable that the essential of the particles, i.e. at least 80% by number, have a size DMET of less than or equal to 7 nm, more particularly less than or equal to 6 nm.
Typically, at least 90% and more particularly at least 95% of the particles have a size DMET of less than or equal to the aforementioned values.
This size DMET may be detected by analyzing the dispersion with transmission electron microscopy (TEM), used in an imaging mode with which the particles may be viewed at high magnification and their size may be measured.
Preferably, and for better accuracy of the measurement of the size of the particles, it is possible to proceed according to the following procedure.
The dispersion according to the invention is diluted beforehand by its solvent so as to obtain an iron mass content of about 0.035%. The thereby diluted dispersion is then placed on an observation grid, like a carbonaceous polymeric membrane supported on a copper grid, and the solvent is evaporated.
For example it is possible to use a transmission electron microscope giving access to magnifications ranging up to 800,000, the acceleration voltage being selected preferably equal to 120 kV.
The principle of the method consists of examining under the microscope various regions (about 10) and of measuring the dimensions of 250 particles, by considering these particles as spherical particles. A particle is estimated as being identifiable when at least half of its perimeter may be defined. The size DMET then corresponds to the diameter of the circle properly reproducing the circumference of the particle. Identification of the particles which may be utilized, may be accomplished by means of a software package such as ImageJ, Adobe Photoshop or Analysis.
A cumulated grain size distribution of the particles is inferred therefrom, which is grouped into 40 grain size classes ranging from 0 to 20 nm, the width of each class being 0.5 nm. The number of particles in each class or for each DMET is the basic datum for representing the number differential grain size distribution.
Moreover, the particles of the dispersion of the invention have a fine grain size as observed by TEM.
They have a medium diameter φ50 preferably comprised between 2 nm and 6 nm, more particularly between 3 nm and 5 nm.
The number median diameter φ50 is the diameter such that 50% of the particles counted on the TEM micrographs have a smaller diameter than this value, and 50% of the counted particles have a larger diameter than this value.
The particles according to the invention generally have a polydispersity index Pn comprised from 0.1 to 0.5.
This polydispersity index Pn is calculated from the number grain size distribution determined by TEM according to the following formula:
φ16 being the diameter for which 16% of the particles have a diameter of less than this value, and φ84 being the diameter for which 84% of the particles have a diameter of less than this value.
This measurement reflects the fact that the particles according to the invention have good monodispersity.
The dispersion state of the solid objects may be characterized by dynamic light scattering (DLS), also called quasi-elastic light scattering (QELS), or further photon correlation spectroscopy. This technique allows measurement of a hydrodynamic diameter Dh of the solid objects, the value of which is highly affected by the presence of aggregates of particles.
Preferably, the solid objects of the invention have a hydrodynamic diameter Dh of less than or equal to 30 nm, preferably less than or equal to 20 nm, preferentially less than or equal to 16 nm, as measured by dynamic light scattering (DLS).
The hydrodynamic diameter Dh of the solid objects of a dispersion according to the invention may be measured on the dispersion of the invention, after dilution of the latter by its solvent so as to attain an iron concentration comprised from 1 to 4 g·L−1.
A light scattering apparatus of the ALV CGS 3 (Malvern) apparatus provided with an ALV series 5000 correlator and with an ALV Correlator software package V3.0 or more. This apparatus uses the so-called <<Koppel cumulants>> data processing method, which gives the possibility of accessing the value of the hydrodynamic diameter Dh.
It is important to conduct the measurement at the temperature (typically 25° C.) corresponding to the viscosity values and to the refractive index values used for the solvent in the calculation of the hydrodynamic diameter and to use a measurement angle typically set to 90°.
It is also recommended to carry out the preparations of the dilution as well as the handling operations under a lamina flow hood in order to avoid contamination of the samples by dust and distort the measurement.
It is considered that the experimental data are validated if the scattered intensity is stable and if the autocorrelation function is without any abnormalities.
Finally, the scattering intensity should be comprised within limits defined for each apparatus.
This feature of the objects of the dispersion contributes to its stability. The individualized nature of the particles also increases the global contact surface area available between the latter and the soots and thus contributes to improving the catalytic activity of the dispersion according to the invention.
The dispersions according to the invention may further comprise in the organic phase, particles of an iron compound in the amorphous form, notably particles for which the size is greater than or equal to 4 nm.
The amorphous nature of an iron compound may be shown by XRD analysis of this compound, when no characteristic peak of any crystalline iron phase is observed.
Preferably, the particles of an iron compound in the amorphous form represent at most 75% by number of the total amount of iron particles of the dispersion.
For particles with a size greater than or equal to 4 nm, the particles of an iron compound in the amorphous form represent at most 50% by number of the total amount of iron particles with a size greater than or equal to 4 nm, and preferably at most 40% by number.
The dispersions according to the invention have an iron compound mass concentration which may be of at least 2%, more particularly at least 5%, this concentration being expressed in iron metal mass based on the total mass of the dispersion.
This concentration may generally range up to 20%.
The iron content may be determined by any technique known to one skilled in the art such as by the measurement by X fluorescence spectroscopy directly applied on the dispersion according to the invention.
The dispersions according to the invention may be prepared according to a method including the following steps:
a) putting into contact in an aqueous phase a base and a mixture comprising an Fe(II) salt and an Fe(III) salt according to a molar ratio Fe(II)/Fe(III) comprised from 0.45 to 0.55, preferably about equal to 0.5, advantageously equal to 0.5, by maintaining the pH of the aqueous phase at a pH value of more than 11.5, whereby a precipitate is obtained; and
b) putting into contact the thereby obtained precipitate, optionally separated from the aqueous phase, with an organic phase based on the solvent, in the presence of an amphiphilic agent, whereby the dispersion is obtained in an organic phase.
In step a) of the method, a base and a mixture comprising an Fe(II) salt and an Fe(III) salt are put into contact, according to a molar ratio Fe(II)/Fe(III) comprised from 0.45 to 0.55, preferably about equal to 0.5, advantageously equal to 0.5, in an aqueous phase, typically an aqueous solution of the base and of the iron salt.
As a base, it is notably possible to use compounds of the hydroxide type. Mention may be made of alkaline or earth alkaline hydroxides and ammonia. It is also possible to use secondary, tertiary or quaternary amines.
As an iron salt, it is possible to use any water-soluble salt. As an Fe(II) salt, mention may be made of ferrous chloride FeCl2. As an Fe(III) salt, mention may be made of ferric nitrate Fe(NO3)3.
During step a), the reaction taking place between the Fe(II) salt, the Fe(III) salt and the base is generally accomplished under conditions such that the pH of the formed reaction mixture remains greater than or equal to 11.5, during the putting into contact of the iron salts and the base in the reaction medium.
Preferably, during step a), the pH of the reaction mixture is maintained at a value greater than or equal to 12. This pH value is typically comprised from 12 and 13.
The putting into contact of the iron salts and of the base in an aqueous phase may be accomplished by introducing a solution of the iron salts into a solution containing the base, for which the pH is of at least 11.5. It is also possible to introduce the iron salts and the base into a solution containing the salts, at a concentration typically less than or equal to 3 mol·L−1, such as for example sodium nitrate, and for which the pH is adjusted beforehand to a value greater than or equal to 11.5. It is possible to achieve the contacting continuously, the pH condition being met by adjusting the respective flow rates of the solution of the iron salts and of the solution containing the base.
It is possible, according to a preferred embodiment of the invention to operate under conditions such that during the reaction between the iron salts and the base, the pH of the aqueous phase is maintained constant. By constant maintaining of the pH is meant a variation of the pH of ±0.2 pH units relatively to the set value. Such conditions may be obtained by adding during the reaction between the iron salts and the base, for example during the introduction of the solution of the iron salts into the solution of the base, an additional amount of base in the aqueous phase.
Within the scope of the present invention, the inventors have observed that the size of the particles may be modulated depending on the pH at which the aqueous phase is maintained. Typically, and without intending to be bound to a particular theory, the size of the particles is all the smaller since the pH of the aqueous phase is high.
The reaction of step a) is generally conducted at room temperature. This reaction may advantageously be achieved under an air or nitrogen atmosphere or a nitrogen/air mixture.
At the end of the reaction of step a), a precipitate is obtained. It is optionally possible to cause ripening of the precipitate by maintaining it for a certain time for example a few hours, in the aqueous phase.
According to a first advantageous alternative of the method according to the invention, the precipitate is not separated from the aqueous phase at the end of step a) and is left suspended in the aqueous phase of the reaction of step a).
According to another alternative of the method according to the invention, the method includes, after step a), and before step b), a step a) for separating the formed precipitate at the end of step a) of the aqueous phase.
This separation step a) is carried out by any known means.
The separated precipitate may then be washed with water for example. Preferably, the precipitate is not subject to any drying or freeze-drying step or any operation of this type.
The precipitate may optionally be resuspended in a second aqueous phase.
In order to obtain a dispersion in an organic phase, during step b), the precipitate obtained at the end of step a), whether it is separated from the aqueous phase or not, is put into contact with the organic phase in which the dispersion is desirably obtained.
This organic phase is of the type of the one which was described above.
The putting into contact of step b) is accomplished in the presence of the aforementioned amphiphilic agent, optionally, after neutralization of the suspension obtained at the end of step a).
Preferably, the molar ratio between the number of moles of amphiphilic agent and the number of moles of iron is comprised from 0.2 to 1, preferentially comprised from 0.2 to 0.8.
The amount of organic phase to be incorporated is adjusted so as to obtain an oxide concentration as mentioned above.
The order of introduction during step b) of the different elements of the dispersion is indifferent.
The obtained precipitate, the amphiphilic agent and the organic phase may be put into contact simultaneously.
It is also possible to produce the premix of the amphiphilic agent and of the organic phase.
The contacting between the precipitate and the organic phase may be accomplished in a reactor which is under an atmosphere of air, nitrogen or of an air-nitrogen mixture
Although the contacting between the precipitate and the organic phase may be accomplished at room temperature, about 20° C., it is preferable to operate at a temperature selected in an interval ranging from 30° C. to 150° C., advantageously between 40° C. and 100° C.
In certain cases, because of the volatility of the organic phase, its vapors should be condensed by cooling to a temperature below its boiling point.
The reaction mixture resulting from the precipitate, from the organic phase and from the amphiphilic agent is maintained with stirring during the whole duration of the heating.
In the case of the first alternative wherein the precipitate has not been separated from the aqueous phase at the end of step a), when heating stops, the presence of two new phases is noted: an organic phase containing dispersion of particles and a residual aqueous phase. The organic phase is then separated, containing the dispersion of particles and also the residual aqueous phase according to conventional separation techniques such as for example decantation or centrifugation.
Regardless of the alternative of the method, according to the present invention, at the end of step b), organic dispersions are obtained having the aforementioned characteristics.
The dispersions further comprising particles of an iron compound in an amorphous form, may be obtained by mixing a first dispersion of particles of an iron compound in the amorphous form in an organic phase with a second dispersion of particles of an iron compound in the crystallized form, this second dispersion being of the type according to the first embodiment of the invention.
As a first dispersion of particles of an iron compound in the amorphous form, those described in WO 2003/053560 for example may be used.
Preferably dispersions are mixed for which the organic phases are identical.
The dispersions according to the invention may be used as a fuel additive for internal combustion engines, more particularly as an additive of gas oils for a diesel engine or as additives of gasolines for certain gasoline engines emitting soot or carbonaceous particles, and for example as additives for biofuels.
They may more generally be used as combustion additives in liquid combustible materials or fuels of energy generators such as internal combustion engines (positive ignition engine), electric generating sets, oil burners, or jet propulsion engines.
The object of the invention is also an additived fuel for internal combustion engines comprising a fuel and a dispersion according to the invention.
The additived fuels according to the invention may be used in combination with a PF not containing any catalyst, or else with a PF containing a catalyst such as an CSF.
The nature of the catalyst making up the CSF may be of any type, notably based on precious metals such as platinum or palladium associated with different supporting or binding materials such as alumina. Materials which may be reduced like oxides based on rare earths, such as cerium oxide or oxides based on manganese may also be associated.
The organic dispersions according to the invention have the particularity, once additived with the fuel, of not consequently reducing the stability of said fuel, in particular when the latter contains not very stable fractions such as fractions of biofuels like methyl esters of vegetable oils. The stability of the fuel may be measured through its resistance to oxidation.
For this, several types of test are known to the profession. It is possible to mention the test based on the NF EN 15751 standard (Fuels for automobiles—Methyl esters of fatty acids (FAME) and mixtures with gas oil—Determination of the stability to oxidation by an accelerated oxidation method) consisting of oxidizing the heated fuel with bubbling of air. The vapors produced during the oxidation process are condensed in water. An increase in the electric conductivity of this water expresses solubilization of volatile acid compounds formed during the oxidation process of the fuel and therefore from its oxidation. This is then referred to as the induction time, a time representing the duration of heating required for occurrence of a fast increase in the electric conductivity. The higher this induction time, the more the fuel resists to oxidation. This test is also called a RANCIMAT test.
It was observed that the dispersions according to the invention are stable, compatible with fuels, notably biofuels, efficient for regenerating the PFs at a low dosage and at low temperature and have a very good compromise between fuel compatibility, notably the maintaining of good properties of resistance to oxidation of the (bio) fuel, and efficiency for regenerating the PF.
The dispersions according to the invention or a Fuel Borne Catalyst (FBC), may be additived to fuels according to any means known to one skilled in the art, both by a vectorization device loaded on-board a vehicle but also directly additived in the fuel before the latter is introduced on the vehicle. The latter case may advantageously be used in the case of vehicle fleets equipped with PFs and having their own gas station for refilling with fuel.
The devices loaded on-board the vehicle may notably be devices comprising a tank, giving the possibility of loading on-board a volume of the dispersion according to the invention and giving the possibility of covering a certain range, as well as a means for vectorizing the dispersion towards the fuel like a metering pump injecting a defined amount of the dispersion into the fuel tank of the vehicle and a tool for driving this vectorization means.
The engine may be continuously fed with a fuel additive with FBC, the concentration may be stable or variable over time. The engine may also be alternatively fed with an additived and non-additived fuel. The amount of FBC to be added to the fuel may widely vary depending on different parameters such as the characteristics of the engine and of its equipment, its polluting emissions, notably the amount of emitted soots, the architecture of the exhaust and depolluting line, notably the use of a PF or of a CSF containing a catalyst and its proximity to the manifold of the engine, the means allowing an increase in the temperature for triggering regeneration or else in the geographical area in which the vehicle will circulate, the latter defining the quality of the fuel which the vehicle will use.
The FBC may also be injected into the exhaust line above the PF, preferably with a means allowing final dispersion of the particles into the bed of soots. This case is particularly adapted to the case when the regeneration of the PF is accomplished by direct injection of the fuel into the exhaust line upstream from the PF, whether this fuel is burned on an oxidation catalyst upstream from the PF or else by a burner or by any other means.
The fuels suitable for preparing an additived fuel according to the present invention notably comprise commercially available fuels and in certain embodiments, all the commercially available gas oil fuels, and/or biofuels.
Preferably, the fuels comprised in the additived fuel is selected from the group formed by gas oils and biofuels.
The gas oil fuels may also be called diesel fuels.
The fuels based on bio-additives are also called biofuels.
The suitable fuels for applying the invention are not too limited, and are generally liquid at room temperature, for example from 20 to 30° C.
The liquid fuel may be a fuel of the hydrocarbon type, a fuel of a type other than a hydrocarbon, or one of their mixtures.
The fuel of the hydrocarbon type may be a petroleum distillate, notably a gasoline according to the definition given by the ASTM D4814 standard or a gas oil fuel according to the definition given by the ASTM D975 standard or the European standard EN590+A1.
In an embodiment, the liquid fuel is a gasoline, in another embodiment, the liquid fuel is a lead-free gasoline.
In another embodiment, the liquid fuel is a gas oil fuel.
The fuel of the hydrocarbon type may be a hydrocarbon prepared by a method for transforming a gas into a liquid in order to include for example hydrocarbons prepared by a process such as the Fischer-Tropsch process.
In certain embodiments, the fuel applied in the present invention is a gas oil fuel, a gas oil biofuel or combinations thereof.
The fuel of the type other than a hydrocarbon may be a composition containing oxygen atoms, which is often called an oxygenation product, which comprises an alcohol, an ether, a ketone, an ester of a carboxylic acid, a nitroalkane, or one of their mixtures. The fuel of a type other than a hydrocarbon may for example comprise methanol, ethanol, methyl-t-butyl ether, methyl ethyl ketone, oils and/or trans-esterified fats of vegetable or animal origin such as rape seed methyl ester and soya methyl ester, and nitromethane.
The mixtures of fuels of the hydrocarbon type and of the type other than a hydrocarbon may comprise for example gasoline and methanol and/or ethanol, gas oil fuel and ethanol, and gas oil fuel and a trans-esterified vegetable oil such as rape seed methyl ester and other bio-derived fuels.
In an embodiment, the liquid fuel is a water emulsion in a fuel of the hydrocarbon type, a fuel of a type other than a hydrocarbon, or one of their mixtures.
In several embodiments of this invention, the liquid fuel may have a sulfur content, on a basis by weight, which is of 5,000 ppm or less, a 1,000 ppm or less, or 300 ppm or less, 200 ppm or less, 30 ppm or less or 10 ppm or less.
The liquid fuel of the invention is present in an additived fuel according to the invention in a major amount, i.e. generally greater than 95% by weight, and in other embodiments, it is present in an amount of more than 97% by weight, of more than 99.5% by weight or more than 99.9% by weight.
The fuels suitable for applying the present invention optionally comprise one or several additional performance additives, solvents or diluents. These performance additives may be of any type and for example allow improvement in the distribution of the fuel in the engine and/or the improvement of the performances of the operation of the engine and/or improvement in the stability of the operation of the engine.
As an example and without being limited, it is possible to mention antioxidants like sterically hindered phenol, detergent and/or dispersant additives such as nitrogen-containing detergents or succinimides or further agents improving cold flow such as an esterified copolymer of maleic anhydride and styrene.
According to an advantageous feature of the additived fuels according to the invention, the iron content, expressed as ppm by weight of metal iron relatively to the total weight of the fuel, is comprised from 1 to 30 ppm, and preferably from 2 to 20 ppm of metal iron.
Examples will now be given.
Preparation of the Solution of Iron Precursors
A liter of solution is prepared in the following way: 576 g of Fe(NO3)3 are mixed with 99.4 g of FeCl2, 4H2O. The mixture is completed with distilled water in order to obtain one liter of solution. The final concentration of this solution of iron precursors is 1.5 mol·L−1 of Fe.
Preparation of the Soda Solution
A solution of NaOH at 6 mol·L−1 is prepared in the following way: 240 g of soda tablets are diluted in distilled water in order to obtain one liter of solution.
Into a reactor of one liter equipped with a stirring system, a tank bottom is introduced, consisting of 400 ml of a solution of sodium nitrate NaNO3 at 3 mol·L−1. The pH of the solution is adjusted to 13 by a few drops of soda at 6 mol/L. The formation of the precipitate is accomplished by simultaneous addition of the solution of iron precursors and of the soda solution prepared beforehand. The flow rates for introducing both of these reagents are adjusted so that the pH is maintained constant and equal to 13 at room temperature.
823.8 g of the solution obtained by precipitation (i.e. 21.75 g of an Fe2O3 equivalent or further 0.27 mol of Fe), neutralized beforehand, are redispersed in a solution containing 24.1 g of isostearic acid (Prisorine 3501, a cut provided by Croda) and 106.4 g of Isopar L. The suspension is introduced into a jacketed reactor equipped with a thermostated bath and provided with a stirrer. The reaction set is brought to 90° C. for 4 h.
After cooling, the mixture is transferred into a test tube. Demixing is observed and a 500 mL aqueous phase and a 100 mL organic phase are collected. This organic dispersion has an iron mass content of 10%, expressed in metal iron mass based on the total mass of the collected dispersion.
The obtained product is stable for at least one month of storage at room temperature, no decantation is observed.
The same procedure as the one of Example 1 is followed, except for, before introducing the reagents in the tank bottom, the pH of the sodium nitrate solution being adjusted to 11 and during the formation of the precipitate, the flow rate for introducing for iron precursors and the solution of soda are adjusted so that the pH is maintained constant and equal to 11 at room temperature.
Preparation of an Iron Acetate Solution
412.2 g of Fe(NO3)3. 5H2O at 98% are introduced into a beaker and distilled water is added thereto up to a volume of 2 liters. The solution is a 0.5M Fe solution. 650 mL of 10% ammonia are added dropwise with stirring and at room temperature, in order to obtain a pH of 7.
The mixture is centrifuged for 10 minutes at 4,500 rpm and then the mother waters are removed. The solid is resuspended in distilled water to a total volume of 2,650 mL. The mixture is stirred for 10 mins, and then centrifuged for 10 mins at 4,500 rpm. The mother waters are removed and the solid is resuspended in distilled water to a total volume of 2,650 mL. Stirring is left for 30 mins. 206 mL of concentrated acetic acid are then added. Stirring is left overnight. The obtained iron acetate solution is limpid.
The formation of the precipitate is then achieved in a continuous assembly comprising:
The iron acetate solution and the 10% ammonia solution are added together. The flow rates of both solutions are set so that the pH is maintained constant and equal to 8.
The obtained precipitate is separated from the mother waters by centrifugation at 4,500 rpm for 10 mins. 95.5 g of hydrate are collected with 21.5% of dry extract (i.e. 20.0 g of equivalent Fe2O3 or 0.25 mol of Fe) and are then redispersed in a solution containing 39.2 g of isostearic acid in 80.8g of Isopar L. The suspension is introduced into a jacketed reactor equipped with a thermostatic bath and provided with a stirrer. The reaction set is brought to 90° C. for 5 h 30mins.
After cooling it is transferred into a test tube. Demixing is observed and a 50 mL aqueous phase and a 220 mL organic phase are collected. The collected organic dispersion has a 10% iron mass content, expressed as a mass of metal iron relatively to the total mass of the collected dispersion.
The XRD analysis was carried out according to the indications given in the description.
It is seen that the peaks of the diffractograms of the dispersion of Example 1 and of the dispersion of Example 2 actually correspond to the diffraction peaks XRD characteristics of the crystallized magnetite and/or maghemite phase (sheet ICDD 01-088-0315).
The diffractrogram of the dispersion of Example 3 does not have any significant XRD peak, which allows the conclusion to be drawn that the iron phase is in an amorphous form.
The calculation of the crystallite size according to the method shown earlier leads to crystallite sizes of 4 nm for Example 1 which are compliant and 9 nm for Example 2 which are non-compliant, respectively.
Analysis by TEM was carried out according to the indications given in the description.
The characteristics from this TEM counting: percentage of particles less than 7 nm, φ50, polydispersity Pn are reported in Table 1.
DLS analysis was carried out according to the indications given in the description.
The average hydrodynamic diameters Dh in intensity are reported in Table 2.
An additived fuel is prepared in order to measure the compatibility of the dispersions according to the invention with said fuel.
For this, a certain amount of dispersion is added to the fuel in order to attain a metal iron mass concentration of 7 ppm in the fuel. The fuel used here is a fuel containing approximately 11% by mass of biofuel (fatty acid methyl ester or FAME) (Table 3).
The test is based on the NF EN 15751 standard (Fuels for automobiles—Fatty acid methyl esters (FAME) and mixed with gas oil—Determination of the oxidation stability by an accelerated oxidation method).
For this test, a dry air flow (10 L/h) bubbles in 7.5 g of the fuel heated to 110° C. The vapors produced during the oxidation process are carried away by the air into a cell containing demineralized water and an electrode measuring the conductivity of water. This electrode is connected to a measurement and recording system. This system indicates the end of the induction period when the conductivity of water increases rapidly. This rapid increase in the conductivity is caused by solubilization in the water of volatile carboxylic acids formed during the oxidation process of the fuel.
Table 4 shows that the degradation of the fuel is very low when a dispersion of iron particles in the crystallized form is used, induction times close to 33-35 h are measured for a fuel additive with the dispersion of Example 1 (particles in crystallized form, 4 nm size), and for a fuel additive with the dispersion of Example 2 (particles in crystallized form, 9 nm size).
Conversely, the induction time of a fuel additive with the dispersion of Example 3 (particles in amorphous form) leads to a greater degradation, the induction time under these conditions dropping down to 19.8 h.
The efficiency of the dispersion described in the previous examples for regenerating a particle filter (PF) was measured through engine tests for regenerating PF. For this, a diesel engine provided by the Volkswagen group (4 cylinders, 2 liters, turbocompressor with air cooling, 81 kW) was used on an engine test bench.
The exhaust line mounted downstream is a commercial line consisting of an oxidation catalyst containing a washcoat based on platinum and alumina followed by an PF in silicon carbide (PF : total volume 2.52 L, diameter 5.66 inches, length 5.87 inches).
The fuel used is a commercial fuel fitting the EN590 DIN 51628 standard containing less than 10 ppm of sulfur and containing 7% by volume of FAME. For these tests, the fuel is additived with different dispersions of Examples 1, 2 and 3. The added content is adjusted so as to add into the fuel an amount of dispersion corresponding to 5 ppm by weight (Examples 1 and 3) or 7 ppm by weight (Example 2) of iron expressed in the form of metal iron based on the total mass of fuel. As a comparison, a fourth test was conducted with the same fuel but not additived with a dispersion.
The test is conducted in two successive steps: a step for loading the PF, followed by a step for regenerating the latter. The conditions of both of these steps are strictly identical for the four tests, except for the fuel used (either additived or not).
The loading phase is carried out by operating the engine at a speed of 3,000 revolutions/minute (rpm) and by using a torque of 45 Nm for approximately 6 hours. This loading phase is stopped when 12 g of particulate phase are loaded in the PF. During this phase the temperature of the gas upstream from the PF is from 230 to 235° C. Under these conditions, the emissions of particles are of about 2 g/h.
After this loading phase, the PF is disassembled and weighed in order to check the mass of loaded particles during this phase (amount of particulate phase in the PF after loading, of Table 5).
The PF is then reassembled on the bench and heated by the engine which is put back for 30 minutes under the operating conditions of the loading (3,000 rpm/45 Nm).
The conditions of the engine are then modified (torque 80 Nm/2,000 rpm) and post injection is requested to the central electronic unit of the engine (ECU) which allows the temperature to be raised upstream from the PF to 450° C. and starting the regeneration of the PF. These conditions are maintained for 35 minutes (2,100 seconds), this time being counted from the starting of the post injection.
The PF regeneration efficiency is measured through two parameters:
Generally, the higher these parameters, the more the regeneration is efficient.
The results are grouped in Table 5.
It is seen that the presence of an additive in the fuel gives the possibility of obtaining regeneration of the PF at 450° C. since 94 to 97% of the soots are burnt after 35 minutes at 450° C. while in the absence of any additive, only 18% of the soots are burnt. The same applies if the pressure drop is observed on the PF, which is more greatly reduced in the presence of an additive: in both cases it drops by about 85 mbars to about 30 mbars while without any additive the pressure drops after 35 minutes at 450° C., remains greater than 65 mbars expressing non-complete regeneration.
When the dispersions are compared, it is seen that the dispersion of Example 1 (dispersion of 4 nm crystallized particles) leads to regeneration kinetics close to those of Example 3 (dispersion of amorphous particles) and this for a low dosage corresponding to 5 ppm by weight of iron. Conversely, in order to have the same kinetics of the dispersion of Example 2 (dispersion of 9 nm crystallized particles), the additive amount has to be increased and attain the equivalent of 7 ppm by weight of metal iron in the fuel which demonstrates the lower efficiency of dispersions with crystallized particles of great size.
The whole of the Examples illustrates that the dispersions of crystallized particles of magnetite and/or maghemite of small size (here 4 nm) may be very efficient at a low dosage while not notably degrading the fuel.
| Number | Date | Country | Kind |
|---|---|---|---|
| 1061061 | Dec 2010 | FR | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2011/073279 | 12/19/2011 | WO | 00 | 9/24/2013 |
