Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
  • C10L1/328—Oil emulsions containing water or any other hydrophilic phase

Definitions

• the present invention relates to a fuel consisting of an emulsion of water and liquid hydrocarbons, intended for use in engines and thermal machines. More specifically, the present invention relates to a water / hydrocarbon emulsified fuel, the content of certain paraffins in the hydrocarbon phase of which makes it possible to reduce emissions during combustion.
• Patent application DE 3023372 describes a fuel for diesel engines consisting of an emulsion comprising at least 80% by volume of hydrocarbons and 12 to 20% by volume of water, as well as from 0.5 to 1.5% by volume of an emulsifying agent which is an ether of alkylphenol and polyglycol.
• Hydrocarbons are a mixture of at least 10% by volume of a "medium oil” (of the type of conventional gas oils) and at most 90% by volume of a “heavy oil” which may consist in particular, in whole or in part, of vegetable oil.
• the main advantage of this fuel is that it saves substantially the cuts of hydrocarbons at the base of conventional gas oils, by partially replacing them with two other constituents (water and vegetable oils).
• the present invention aims to provide an emulsified fuel based on hydrocarbons and water, which makes it possible to further reduce the polluting emissions compared to the emulsified fuels known in the prior art.
• the Applicant has discovered that, surprisingly, these emissions could be significantly reduced provided that the hydrocarbons entering into the composition of the emulsion contain a substantial amount of a particular family of paraffins, namely normal paraffins (paraffins linear) in C8 to C22 (i.e. whose skeleton is made up of 8 to 22 carbon atoms). Mixtures of such normal paraffins are contemplated.
• the present invention relates to an emulsified fuel containing a liquid hydrocarbon phase, an aqueous phase and at least one emulsifying additive, and which has a water / hydrocarbon weight ratio ranging from 5/95 to 35/65. This fuel is characterized in that the hydrocarbon phase contains from 5 to 35% by weight of normal C8 to C22 paraffins.
• the fuel according to the present invention makes it possible to significantly reduce the emissions during combustion in a heat engine or a boiler, in particular the emissions of nitrogen oxides and solid particles. This effect is all the more important when said normal paraffins are in C13 to C19.
• the hydrocarbon phase contains from 5 to 35% by weight of normal C13 to C19 paraffins.
• the presence in the hydrocarbon phase of the normal paraffins above has been found to have an effect particularly beneficial on the time of auto-ignition and the cetane number of the fuel.
• This advantage is particularly appreciable when said fuel is a fuel for diesel vehicles, since these parameters represent the quality of fuel combustion in a standard diesel engine.
• the implementation of the invention makes it possible, by comparison with a conventional water / hydrocarbon emulsion which is identical, to gain up to 10 points of cetane index.
• the present invention has been found to have a beneficial effect on the stability of the emulsion, as measured by centrifugation according to standard NF M07 101.
• the stability on storage both at room temperature and under hot conditions (75 ° C) is significantly improved.
• the hydrocarbon phase may consist of any mixture of hydrocarbons, provided that it contains the required normal paraffins in an appropriate quantity.
• the hydrocarbon phase comprises at least one petroleum cut of the gasoline, diesel or kerosene type, selected so that it contains from 5 to 35% by weight, preferably from 8 to 20 % by weight, even more preferably from 10 to 20% by weight of normal paraffins in C8 to C22, preferably in C13 to C19.
• the hydrocarbon phase consists of a conventional hydrocarbon fuel to which has been added at least one cut rich in normal paraffins.
• the hydrocarbon phase then comprises a mixture consisting of one or more cuts of hydrocarbons and at least one cut rich in normal paraffins in C8 to C22, preferably in C13 to C19.
• “rich” is meant that said cut contains at least 50% by weight of said normal paraffins, preferably at least 80% by weight, even more preferably at least 90% by weight.
• Said cut rich in normal paraffin is then mixed with the cut (s) of hydrocarbons according to their respective contents of normal paraffins, in proportions such that the resulting hydrocarbon phase contains from 5 to 35% by weight, preferably from 8 to 20% by weight, even more preferably from 10 to 20% by weight of normal paraffins in C8 to C22, preferably in C13 to C19.
• Said cut rich in normal paraffins can be of various origins.
• it may be a cut of petroleum origin, obtained during petroleum refining operations.
• Certain cuts such as gasolines, kerosene or even light gas oils can, in a manner known per se, contain significant amounts of normal-paraffins.
• gasolines, kerosene and distillates “straight run” (resulting directly from the distillation of crude oil), or those resulting from the processes of catalytic cracking, hydrocracking, hydro-treatment. It is then possible to fractionate such sections by distillation, so as to isolate a section containing a substantial quantity of the normal paraffins required in the present invention.
• said cut rich in normal paraffins comprises synthetic paraffins obtained by oligomerization of olefins comprising from 2 to 5 carbon atoms, or by Fischer-Tropsch synthesis from light hydrocarbons such as methane, gas natural.
• said cut rich in normal paraffins comprises at least one oil and / or animal or vegetable hydrotreated fat.
• complete hydrotreatment of the triglycerides of fatty acids contained in animal or vegetable fats makes it possible, by hydrocracking the triglyceride structure and complete hydrogenation of the fatty acids, to obtain cuts of normal paraffins under particularly pure form, that is to say almost free from other hydrocarbons.
• the starting oil or fat can be advantageously chosen from: vegetable oils such as, for example, rapeseed, soybean, sunflower, palm, canola oils, oils extracted from resinous trees (in particular coniferous conifers) ; animal fats such as for example purified fats (“yellow grease”), tallow, poultry fats; used edible oils or fats, such as those recovered from catering, and which generally comprise a mixture of animal fats and vegetable oils; and mixtures of the above products.
• vegetable oils such as, for example, rapeseed, soybean, sunflower, palm, canola oils, oils extracted from resinous trees (in particular coniferous conifers)
• animal fats such as for example purified fats (“yellow grease”), tallow, poultry fats
• used edible oils or fats such as those recovered from catering, and which generally comprise a mixture of animal fats and vegetable oils; and mixtures of the above products.
• the hydrocarbon fraction is advantageously chosen from the bases used in the composition traditional fuels, and which include in particular petrol cuts (distillation range generally included in the range 25 to 200 ° C), middle distillates such as for example kerosene cuts (distillation range generally included in the range 160 to 240 ° C) and diesel fractions (distillation range generally included in the range 160 to 400 ° C), biofuels, and mixtures of such fractions.
• petrol cuts distillation range generally included in the range 25 to 200 ° C
• middle distillates such as for example kerosene cuts
• diesel fractions diesel fractions
• biofuels and mixtures of such fractions.
• the cut of hydrocarbons to which is mixed the cut rich in normal paraffins to obtain the hydrocarbon phase according to the invention, can be chosen from the cuts mentioned above for fuels, but also among intermediate vacuum distillates (distillation range generally included in the range 350 to 450 ° C), heavy vacuum distillates (distillation range generally included in the range 400 to 550 ° C), or even distillation residues , and generally among all cuts traditionally used in fuels such as for example FOD (Domestic Fuel Oil), fuel oils, fuel oils, heating oils and mixtures of such cuts.
• the fuel according to the invention is in the form of an emulsion of fine droplets of aqueous phase regularly dispersed in the hydrocarbon phase.
• the average diameter of the droplets of aqueous phase regularly dispersed in the hydrocarbon phase is less than or equal to 5 ⁇ m, preferably to 3 ⁇ m, even more preferably to 1 ⁇ m.
• the particle size profile of the drop sizes is of the monodispersed type around a value of approximately 0.5 ⁇ m. The above values of average droplet size correspond to measurements carried out by the technique of laser granulometry.
• the emulsion contains at least one emulsifying agent.
• emulsifying agent denotes any additive or mixture of additives having surfactant properties, capable of guaranteeing the stability of the fine droplets of aqueous phase in the organic phase.
• emulsifiers such as, for example, but not limited to compounds chosen from fatty acids, fatty acid derivatives, alcohols fatty, ethoxylated fatty amines, polyol esters, functionalized polymers and their mixtures.
• the emulsifying agent contains at least one nonionic organic emulsifying additive, preferably of natural origin.
• nonionic organic emulsifying additive examples include fatty acids and their derivatives, polyol esters, functionalized polymers.
• the emulsifying agent consists of a mixture of at least two emulsifying additives. Examples of such emulsifying agents are described in patent applications WO 97/34969 and WO 01/48123.
• the content of emulsifying agent in the fuel depends, in a manner known per se, on the nature and the effectiveness of this agent.
• the additives used as emulsifying agents are generally incorporated in the emulsions in contents which can range from 0.5 to 5% by weight.
• the fuel according to the invention has an emulsifying agent content of between 1 and 3% by weight.
• the emulsified fuel according to the present invention can advantageously contain one or more biocidal agents, preferably in its aqueous phase.
• This biocidal agent is preferably a bactericide and / or a fungicide.
• biocidal agents let us cite isothiazolones and their chlorinated derivatives, benzalkonium chlorides, organic peroxides, isothiocyanates.
• the emulsified fuel can also include at least one anti-freeze agent.
• anti-freeze agents it is possible to use, for example, alcohols, glycols, glycol or alcohol derivatives, saline solutions. It can also contain at least one anti-soot agent.
• anti-soot agent As an example of such agents, mention may be made of additives constituted by one or more metallic or alkaline-earth catalysts capable of promoting the post-combustion reactions of the soot.
• the preferred catalysts are based on magnesium, calcium, barium, cerium, copper, iron or their mixtures.
• catalytic promoters for destroying soot are all the easier to introduce since they are generally compounds whose salts are soluble in water, therefore in the aqueous phase of the emulsions according to the invention.
• its sulfur content determined according to standard NF M 07-100, is preferably less than or equal to 350 ppm, preferably less than or equal to 50 ppm, and even more preferably less than or equal to 10 ppm.
• the emulsified fuel according to the invention preferably contains one or more other additives, which can be any additive usually used in fuels, including for example, but not limited to: - one or more procetane additives , such as, for example, alkyl nitrates in which the linear or branched, saturated or unsaturated (preferably branched and saturated) alkyl radical contains from 3 to 20 and preferably from 5 to 15 carbon atoms (in particular the 2-ethylhexyl nitrate), organic peroxides and in particular aryl peroxides in which the aryl group is a benzyl group or a substituted benzyl group (for example benzoyl peroxide), or the alkyl peroxides in which the linear or branched, saturated or unsaturated (preferably branched and saturated) alkyl radical contains from 2 to 20 and preferably from 2 to 15 carbon atoms (for example tert-butyl peroxide);
• procetane additives such as
• one or more filterability additives such as, for example, ethylene / vinyl acetate (EVA), ethylene / vinyl propionate (EVP), ethylene / vinyl ethanoate (EVE), ethylene / methyl nethacrylate (EMMA), ethylene copolymers / alkyl fumarate; one or more anti-foam additives, such as for example polysiloxanes, oxyalkylated polysiloxabes, fatty acid amides;
• EVA ethylene / vinyl acetate
• EVE ethylene / vinyl propionate
• EVE ethylene / vinyl ethanoate
• EMMA ethylene / methyl nethacrylate
• anti-foam additives such as for example polysiloxanes, oxyalkylated polysiloxabes, fatty acid amides
• detergent and / or anti-corrosion additives such as for example amines, succinimides, alkenyl succinimides, polyalkyl-amines, polyalkyl-polyamines and polyether-amines;
• lubricating or anti-wear additives such as for example fatty acids and their ester or aide derivatives, mono- and polycyclic carboxylic acids and their ester or amide derivatives;
• cloud point additives such as for example long chain olefin terpolymers / (meth) acrylic ester / maleimide, esters of fumaric or maleic acid esters.
• anti-sedimentation additives such as, for example, (meth) acrylic acid / alkyl (meth) acrylate copolymers amidified with a polyamine, polyamine alkenyl succinimides, derivatives of phthalamic acid and fatty amine to double chain;
• one or more polyfunctional additives for cold operability such as for example polymers based on olefin and alkenyl nitrate.
• the emulsified fuel according to the invention makes it possible to reduce the rates of incorporation into such additives, or, at an equal rate of procetane additive, to obtain more efficient fuels.
• This synergistic effect is particularly effective when the ratio between the mass content of the hydrocarbon phase in normal paraffins in C8 to C22 (preferably in C13 to C19) and the mass content of the fuel in procetane additives is between 5 / 0.5 and 15 / 0.05, preferably between 5 / 0.3 and 15 / 0.1.
• the fuel according to the invention can be prepared in various ways, and in particular by all the conventional ways of preparing emulsions.
• this is done by prior preparation of the hydrocarbon phase, before emulsifying the latter with the aqueous phase.
• the invention therefore also relates to a process for preparing an emulsified fuel comprising at least the following steps: (a) selection of at least one petroleum cut of gasoline, diesel or kerosene type containing from 5 to 35% by weight, preferably from 8 to 20% by weight, even more preferably from 10 to 20% by weight of normal paraffins in C8 to C22, preferably in C13 to C19; or (a ') mixture of one or more cuts of hydrocarbons and at least one cut containing at least 50% by weight of normal paraffins C8 to C22, preferably C13 to C19, so as to obtain a phase hydrocarbon containing from 5 to
• step (b) can be carried out as described in patent application WO 00/34419, by mixing the emulsifying agent with the hydrocarbon phase, then passing the resulting mixture one or more times through a system. emulsifier supplied with water necessary for the formation of the emulsion. It is also advantageous to carry out step (b) as described in patent application WO 01/36569, by:
• the emulsified fuel according to the present invention can be used in various applications. It can in particular be used as fuel for heat engines, or for fuel cells. Its use as a fuel for diesel engines is particularly advantageous.
• the fuel according to the invention can also be used as fuel for thermal machines such as for example industrial or domestic boilers, ovens, turbines, generators.
• thermal machines such as for example industrial or domestic boilers, ovens, turbines, generators.
• FOD domestic Fuel Oil
• a particularly advantageous use is that as FOD (or Domestic Fuel Oil), that is to say as fuel for domestic boilers.
• the invention relates to a method of reducing emissions from engines or thermal machines, comprising the use of an emulsified fuel as described above.
• Aromatics content (ASTM D5186 standard): 10.5% vol
• Viscosity at 40 ° C (ASTM D445 standard): 2.59 cSt
• a second hydrocarbon phase P2 is prepared from PI, by mixing 74.1 parts by weight of PI with 6 parts by weight of a cut rich in normal paraffins of petroleum origin, consisting of more than 99% by weight of normal paraffin in C14.
• the respective emulsified fuels A1 and A2 are prepared, by emulsifying 80.1% by weight of the respective hydrocarbon phases PI and P2 with
• the emulsifying agent used for this purpose consists of a mixture of three surfactant additives, namely a fatty acid ester of sorbitan, an ethoxylated fatty acid and an ethoxylated fatty alcohol.
• Emulsions Al and A2 are tested as fuel on a “Detroit Diesel Corporation Series 60” diesel engine, according to the test and emission measurement procedures described in the “California Exhaust Emission Standards and Test Procedures for 1985 and Subsequent Model Heavy-Duty Diesel Powered Engines and vehicles ”as incorporated by reference into the California Code of Regulations, Title 13, Section 1956.8 (b).
• This example illustrates the synergistic effect which is exerted on the increase in the cetane number of water / hydrocarbon emulsions, when the emulsion contains both the normal C8 to C22 paraffins considered in the invention and a (or more) procetane additive.
• the hydrocarbon phase consists of 100% of diesel fuel G.
• the hydrocarbon phase consists of a mixture of 90% by weight of diesel fuel G and 10% by weight d 'a rich C cut does normal paraffins.
• Section C consists of hydrotreated animal fat, and comprises more than 95% by weight of normal paraffins in C8 to C22, with a majority of normal paraffins in C15 to C18 inclusive.
• emulsions A4 and A6 0.2% by weight (relative to the total weight of the emulsion) of a conventional procetane additive, consisting of 2-ethyl nitrate, hexyl, are added.
• a conventional procetane additive consisting of 2-ethyl nitrate, hexyl.
• the cetane number of each of the emulsified fuels A3 to A6 was measured, in accordance with the method described in standard ASTM D613. Table I below summarizes the compositions of the emulsified fuels and gives the cetane indices obtained for each.
• the presence in the hydrocarbon phase of a high content of normal paraffins C8 to C22 makes it possible to significantly increase the effect of the procetane additive.
• the addition of 0.2% by weight of procetane additive makes it possible to increase the cetane index by 5.5 points
• adding 0.2% by weight of procetane additive increases the cetane number by 6.6 points.
• the invention therefore makes it possible, with a constant procetane additive content, to increase the performance of the emulsified fuel, or, at constant performance, to reduce the contents of procetane additive.
• This example illustrates the improvement in the stability of the emulsified fuels according to the invention.
• the stability of the emulsified fuels A3 and A5 of Example 2 was determined at room temperature, in accordance with the stability test by centrifugation described in standard NF M07 101.
• the graph presented in FIG. 1 below illustrates the results obtained, in fuel sedimentation term (ie phase shift of the emulsion) during the centrifugation time. The higher the sedimentation rate, the more unstable the emulsion.
• FIG. 1 clearly illustrate the beneficial effect, in terms of stability of the emulsion, of the presence in the hydrocarbon phase of a significant content of normal paraffins in C8 to C22: the emulsion A5, in the phase hydrocarbon which according to the invention has been incorporated a cut C rich in normal paraffins C8 to C22, has a significantly better stability than 1 emulsion A3 whose hydrocarbon phase consists exclusively of a conventional diesel.

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• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Liquid Carbonaceous Fuels (AREA)

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• 2002
  • 2002-07-26 FR FR0209508A patent/FR2842820B1/fr not_active Expired - Fee Related
• 2003
  • 2003-07-25 EP EP03756508A patent/EP1527152A2/de not_active Withdrawn
  • 2003-07-25 MX MXPA05001074A patent/MXPA05001074A/es unknown
  • 2003-07-25 CA CA002492968A patent/CA2492968A1/en not_active Abandoned
  • 2003-07-25 US US10/522,419 patent/US20050262759A1/en not_active Abandoned
  • 2003-07-25 AU AU2003281683A patent/AU2003281683A1/en not_active Abandoned
  • 2003-07-25 WO PCT/FR2003/002359 patent/WO2004011575A2/fr not_active Ceased

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