US20060075680A1 - Water/hydrocarbon emulsified fuel preparation and use thereof - Google Patents

Water/hydrocarbon emulsified fuel preparation and use thereof Download PDF

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Publication number
US20060075680A1
US20060075680A1 US10/525,328 US52532805A US2006075680A1 US 20060075680 A1 US20060075680 A1 US 20060075680A1 US 52532805 A US52532805 A US 52532805A US 2006075680 A1 US2006075680 A1 US 2006075680A1
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fuel according
fuel
ester
alcohol
fatty acid
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Frederic Tort
Laurent Dalix
Gabrielle Laluet
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Total Marketing Services SA
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Total France SA
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    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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 comprising an emulsion of water and liquid hydrocarbons, intended to be used in heat engines and thermal machines. More precisely, the present invention relates to an emulsified water/hydrocarbons fuel that has improved high-temperature stability.
  • fuels have appeared on the market that comprise a mixture generally containing at least 5 wt. % of water and hydrocarbons, maintained as an emulsion by using special compositions of surfactant additives (or emulsifying systems).
  • surfactant additives or emulsifying systems.
  • patent EP 630,398 describes an emulsified fuel based on a hydrocarbon fuel and water, in which the emulsifying system comprises a combination of three additives: sorbitan oleate (preferably sorbitan sesquioleate), polyalkylene glycol (preferably polyethylene glycol) and alkylphenol ethoxylate (preferably nonylphenol ethoxylate).
  • sorbitan oleate preferably sorbitan sesquioleate
  • polyalkylene glycol preferably polyethylene glycol
  • alkylphenol ethoxylate preferably nonylphenol ethoxylate
  • Patent EP 888,421 describes a fuel based on an emulsion of water in at least one hydrocarbon, and containing an emulsifying system comprising at least one ester of sorbitol (preferably selected from the oleates of sorbitan), at least one fatty acid ester preferably selected from the oleates and/or the stearates and/or the ricinoleates of polyethylene glycol, and at least one polyalkoxylated alkylphenol preferably selected from the polyethoxylated nonylphenols and/or octylphenols.
  • an emulsifying system comprising at least one ester of sorbitol (preferably selected from the oleates of sorbitan), at least one fatty acid ester preferably selected from the oleates and/or the stearates and/or the ricinoleates of polyethylene glycol, and at least one polyalkoxylated alkylphenol preferably selected from the polyethoxylated
  • Application WO 01/48123 proposes improving the thermal stability of said emulsified fuels, so as to permit the storage and use of the fuel over a wide temperature range, from ⁇ 10° C. to 70° C.
  • This improvement is obtained by using an emulsifying system comprising at least one ester of sorbitol (preferably sorbitan sesquioleate), at least one polyalkoxylated fatty acid ester (preferably selected from the oleates, stearates and ricinoleates of polyethylene glycol), and at least one polyalkoxylated branched hydrocarbon compound preferably selected from the iso-, di- and trialkylated alcohols, preferably the isotridecyl alcohols containing from 3 to 10 ethoxylated groups.
  • an emulsifying system comprising at least one ester of sorbitol (preferably sorbitan sesquioleate), at least one polyalkoxylated fatty acid ester (preferably selected from the oleates,
  • U.S. Pat. No. 6,371,998 describes a liquid hydrocarbon fuel in which water-containing lipid vesicles have been incorporated.
  • These lipid vesicles are constituted, for example, of 4 wt. % of alcohol polyoxyethylene-10-stearate, 7.2 wt. % of glycerol distearate, 5 wt. % of soya methyl ester, 5 wt. % of sorbitan sesquioleate and 78.8 wt. % of water.
  • patent application WO 01/51593 recommends, for improving the thermal stability over a wide temperature range ( ⁇ 20 to +50° C.) of a fuel based on an emulsion of water and liquid hydrocarbons, using a polymeric emulsifier that can be obtained by reaction between a functionalized polyolefin oligomer and a polyoxyalkylene. That application also describes, for comparison, emulsifying systems comprising 87 wt. % of sorbitan monooleate, 3 wt. % of sorbitan trioleate, and 10 wt. % of castor oil ethoxylated with 10 moles of ethylene oxide.
  • the emulsified fuels described in the prior art prove to have insufficient high-temperature stability.
  • the aqueous and hydrocarbon phases tend to separate quickly when the fuel is held at elevated temperatures, above 60° C., for several hours.
  • this makes the use of these emulsified fuels incompatible with the new engine technologies, such as for example diesel engines equipped with pump-based direct injection systems.
  • the fuel is submitted to temperatures generally above 70° C. and, when the engine is stopped, the emulsion that still remains in the supply system tends to undergo phase separation, especially in the injector pump. This phenomenon causes many problems, including considerable difficulty in restarting the vehicle.
  • the present invention proposes an emulsified fuel based on hydrocarbons and water, which has improved high-temperature stability relative to the emulsified fuels known in the prior art, without degradation of the other properties.
  • the present invention relates to an emulsified fuel containing a major proportion (typically at least 80%, advantageously at least 90%, more particularly at least 95% by weight) of an emulsion of water and liquid hydrocarbons with a water/hydrocarbon weight ratio ranging from 5/95 to 35/65.
  • Said fuel is characterized in that it contains an emulsifying system comprising at least 15 wt.
  • % of a fatty acid ester and (poly)oxyalkylated polyol and of at least one member of the group comprising the esters of fatty acid and of sorbitan and the products of condensation of a succinic acid or anhydride with at least one amine, polyamine, fatty acid, (poly)oxyalkylated fatty acid, alcohol, (poly)oxyalkylated alcohol and mixtures of said compounds.
  • the fuel according to the present invention has excellent thermal stability, permitting its storage and use both at cold or ambient temperature and at elevated temperatures, of the order of 75° C. Notably this makes its use perfectly compatible with the new engine technologies such as direct injection.
  • the emulsified fuel according to the invention contains an emulsifying system comprising at least two compounds, either at least two types of esters, or an ester of fatty acid and of (poly)oxyalkylated polyol and a product of condensation of a succinic acid or anhydride with at least one amine, polyamine, fatty acid, (poly)oxyalkylated fatty acid, alcohol, (poly)oxyalkylated alcohol.
  • the ester of fatty acid and of sorbitan is constituted of an ester of fatty acid and of sorbitan or of a mixture of said esters.
  • sorbitan familiar to a person skilled in the art, denotes a cyclic tetraol which is an anhydride of sorbitol and can be obtained by dehydration of the latter. Tetraol denotes a polyol containing 4 hydroxyl groups. Sorbitan is generally present in chemical equilibrium with sorbitol.
  • Said sorbitan ester can comprise one or more monoesters, one or more polyesters, or a mixture of monoesters and polyesters. It can be obtained for example by esterification of one or more fatty acids and of sorbitan.
  • the fatty acids included in the composition of the sorbitan ester which may be linear or branched, saturated or unsaturated, advantageously contain from 6 to 22 carbon atoms, and preferably from 12 to 18 carbon atoms.
  • said fatty acids can be selected from lauric, palmitic, stearic, oleic, linoleic, linolenic acids and mixtures thereof.
  • said sorbitan ester contains at least one sorbitan oleate.
  • suitable sorbitan oleates are sorbitan monooleate, sorbitan dioleate, sorbitan trioleate, sorbitan tetraoleate, sorbitan sesquioleate.
  • said sorbitan ester comprises at least one ester selected from sorbitan monooleate and sorbitan sesquioleate.
  • the ester of fatty acid and of (poly)oxyalkylated polyol hereinafter designated polyol ester can comprise monoesters, polyesters or a mixture of monoesters and polyesters.
  • the fatty acids included in the composition of each of the ester molecules may be identical or different. Moreover, they may be different from one ester molecule to another so that it is a case of a mixture of polyesters.
  • polyol we mean alcohols containing from 2 to 5 hydroxyl groups, preferably alkylene glycols, glycerol, pentaerythritol, their alkylated derivatives and their mixtures.
  • the fatty acids included in the composition of said polyol ester may be linear or branched, saturated or unsaturated, and advantageously contain from 6 to 22 carbon atoms, and preferably from 12 to 18 carbon atoms.
  • they are selected from the fatty acids that are naturally present, in free or esterified form, in vegetable and/or animal oils, such as for example, and nonlimitatively, lauric, palmitic, stearic, oleic, linoleic, linolenic acids, and mixtures thereof.
  • the polyoxyalkyl groups present in the polyol ester are a chain of identical or different oxyalkyl units, each oxyalkyl unit advantageously containing from 1 to 5 carbon atoms, preferably from 1 to 4 carbon atoms.
  • the polyoxyalkyl groups comprise ethoxy units.
  • the polyoxyalkyl groups comprise at least one polyethoxy group.
  • the average number of moles of oxyalkyl units per mole of ester is advantageously between 3 and 50, and preferably between 10 and 35, in particular when the polyol is glycerol.
  • the polyol ester is constituted completely or partially of a triester of fatty acid(s) and of polyoxyalkylated glycerol or a mixture of said triesters. More preferably, it is constituted completely or partially of a triester of fatty acid(s) and of polyethoxylated glycerol or a mixture of said triesters.
  • Said polyol ester can be obtained for example by polyoxyalkylation of an ester or of a mixture of esters of fatty acid and of the polyol or alternatively by esterification of one or more fatty acids and of one or more polyoxyalkylated derivatives of the polyol.
  • Said polyol ester is advantageously obtained by oxyalkylation of vegetable and/or animal oil.
  • the polyol ester is constituted completely or partially of oxyalkylated vegetable and/or animal oil.
  • Such a product comprises triesters of fatty acids and of polyoxyalkylated polyol (preferably glycerol), generally mixed with monoesters and/or diesters of fatty acids and of (poly)oxyalkylated polyol (preferably glycerol).
  • Said oil can if necessary have undergone a purification treatment, before and/or after its oxyalkylation.
  • suitable vegetable oil among others: colza oil, soya oil, castor oil, sunflower oil, palm oil, oils extracted from resinous trees and the mixtures of said oils.
  • suitable animal oil yellow grease, tallow, poultry fats.
  • the polyol ester is constituted completely or partially of ethoxylated vegetable oil.
  • the polyol ester is a diester of polyalkoxylated alkylene glycol and more particularly the dioleate of polyethoxylated ethylene glycol, notably with molecular weight between 200 and 1000.
  • Said polyol ester is advantageously present in the emulsified fuel according to the invention at a content in the range from 0.5 to 5 wt. %, preferably from 0. 5 to 2 wt. %.
  • the emulsifying system comprises from 15 to 100 wt. % of at least one polyol ester, and of at least one member of the group comprising the sorbitan ester and the products of condensation of a succinic acid or anhydride with at least one amine, polyamine, fatty acid, (poly)oxyalkylated fatty acid, alcohol, (poly)oxyalkylated alcohol and mixtures of said compounds.
  • the emulsifying system according to the invention contains from 15 to 100 wt. % of at least one sorbitan ester combined with at least one polyol ester, according to a weight ratio of sorbitan ester to polyol ester that varies from 20/80 to 80/20 inclusive, preferably from 40/60 to 60/40 inclusive. Even more preferably, the amounts by weight of each of the two types of esters are roughly equal (45/55 to 55/45).
  • the sorbitan ester is advantageously present in the emulsified fuel according to the invention at a content ranging from 0.5 to 5 wt. %, preferably from 0.5 to 2 wt. %.
  • the emulsifying system included in the composition of the emulsified fuel according to the invention also comprises, in addition to the two types of esters, at least one alcohol containing from 3 to 22 carbon atoms, and preferably from 6 to 12 carbon atoms.
  • Said alcohol which is advantageously a monohydric alcohol, may be linear or branched, saturated or unsaturated. Preferably it comprises at least one saturated branched alcohol.
  • particularly suitable alcohols include the ethyl hexanols (for example 2-ethyl hexanol), isopropanol, tert.-butanol, isopentanol, isotridecanol, fatty alcohols (i.e. containing from 12 to 22 carbon atoms).
  • the emulsified fuel according to the invention then contains advantageously from 0.1 to 5 wt. % of said alcohol, preferably from 0.3 to 2%, even more preferably from 0.5 to 1 wt. %.
  • this alcohol performs the role of co-surfactant with respect to said first and second esters, i.e. it facilitates and reinforces the emulsifying power of the latter.
  • this alcohol makes it possible to improve the uniformity in size of the water droplets: the latter are of a more uniform size (more monodisperse distribution) and smaller.
  • the presence of large droplets is thus avoided, which has the immediate effect of improving the fuel's resistance to sedimentation (the phenomenon of accumulation of the water droplets at the bottom of the fuel, which occurs more quickly as the proportion of large droplets increases).
  • the emulsifying system included in the composition of the emulsified fuel according to the invention also comprises from 0 to 85 wt. % of at least one compound that is the product of condensation of a succinic acid or anhydride with at least one amine, polyamine, fatty acid, (poly)oxyalkylated fatty acid, alcohol, (poly)oxyalkylated alcohol and mixtures of said compounds, called condensation product hereinafter.
  • condensation product Preferably, the product of condensation of at least one succinic anhydride with at least one polyamine is used.
  • the succinic acid or anhydride is advantageously substituted by a hydrocarbon radical which is preferably a polymeric radical, for example a polyisobutyl radical.
  • the presence of such a compound in the emulsifying system of the fuel according to the invention offers various advantages. On the one hand, it makes it possible to improve the uniformity of size of the water droplets. On the other hand it promotes compatibility of the emulsified fuel according to the invention with conventional fuels constituted entirely of hydrocarbons, so that these two types of fuels become interchangeable. It thus becomes possible, in a vehicle usually operating with a conventional hydrocarbon fuel, to fill the fuel tank with the emulsified fuel according to the invention without having to purge the fuel distribution system, and vice versa.
  • the emulsifying system contains from 15 to 85 wt. % of at least one polyol ester and from 85 to 15% of at least one condensation product.
  • This combination provides a notable increase in the excellent thermal stability of the emulsion containing esters, during its storage and use both at low temperature and at ambient temperature and finally at high temperatures, of the order of 75° C.
  • the preferred emulsifying system in this form of the invention contains from 20 to 50 wt. % of at least one polyol ester and from 50 to 80% of at least one condensation product.
  • this emulsifying system also has added to it at least one alcohol of the type described previously, i.e. a monohydric alcohol, which can be linear or branched, saturated or unsaturated, containing from 3 to 22 carbon atoms, and preferably from 6 to 12 carbon atoms.
  • a monohydric alcohol which can be linear or branched, saturated or unsaturated, containing from 3 to 22 carbon atoms, and preferably from 6 to 12 carbon atoms.
  • the emulsified fuel according to the invention can contain many other emulsifying agents.
  • a person skilled in the art will be perfectly capable of perfecting the formula of the emulsifying system according to the invention by adding other known emulsifiers, ionic or nonionic, synthetic or of natural origin such as, for example, but nonlimitatively, compounds selected from the fatty acids, derivatives of fatty acids, fatty alcohols, ethoxylated aliphatic amines, esters of polyols, functionalized polymers and mixtures thereof.
  • the hydrocarbon phase of the emulsified fuel according to the invention can be constituted of any mixture of hydrocarbons.
  • hydrocarbon fractions and mixtures of fractions of very diverse origin and nature The choice is dictated essentially by the use for which the fuel is intended, by the availability of the various hydrocarbon fractions, and by economic considerations (cost of the fuel).
  • the hydrocarbon phase advantageously comprises one or more hydrocarbon fractions that occur in the composition of conventional motor fuels, and which can be selected notably from the gasoline fractions (distillation range generally within the range from 25 to 200° C.), middle distillates such as for example the kerosene fractions (distillation range generally within the range from 160 to 240° C.) and gas-oil fractions (distillation range generally within the range 160 to 400° C.), biofuels, and mixtures of said fractions.
  • gasoline fractions distillation range generally within the range from 25 to 200° C.
  • middle distillates such as for example the kerosene fractions (distillation range generally within the range from 160 to 240° C.) and gas-oil fractions (distillation range generally within the range 160 to 400° C.)
  • biofuels and mixtures of said fractions.
  • fractions can be obtained from oil refining, from agriculture (in the case of biofuels), or can be synthetic hydrocarbons (for example obtained by oligomerization of light olefins, or by Fischer-Tropsch synthesis from light hydrocarbons).
  • Biofuel denotes light alcohols (such as ethanol for example), oils of vegetable and/or animal origin and the esters of said oils.
  • the hydrocarbon phase of the fuel according to the invention can thus advantageously contain from 0.1 to 60 wt. %, and preferably from 0.5 to 50 wt. % of biofuel.
  • the preferred biofuels are the esters of alcohols containing from 1 to 4 carbon atoms and of fatty acids or of mixtures of fatty acids containing from 16 to 22 carbon atoms.
  • the biofuels that are particularly preferred are the methyl esters of vegetable oils such as for example, but nonlimitatively, soya, colza, sunflower, olive and palm oils.
  • the hydrocarbon phase can comprise one or more of the aforementioned fractions for the fuels, and/or other fractions if required selected from the intermediate vacuum distillates (distillation range generally within the range 350 to 450° C.), the heavy vacuum distillates (distillation range generally within the range 400 to 550° C.), or even distillation residues, and generally from all the fractions used conventionally in fuels such as for example domestic fuel oil, fuel oils, petroleum residues, heating oils and mixtures of these fractions.
  • distillation ranges are cited with reference to standard ASTM D 86 (distillation of petroleum products).
  • the fuel according to the invention is in the form of an emulsion of fine droplets of aqueous phase dispersed uniformly in the hydrocarbon phase.
  • the average diameter of the droplets of aqueous phase is less than or equal to 5 ⁇ m, preferably to 3 ⁇ m, even more preferably to 1 ⁇ m.
  • the granulometric profile of the sizes of droplets is of the monodisperse type around a value of about 0.5 ⁇ m. The aforementioned values of average droplet size correspond to measurements carried out by laser granulometry.
  • the emulsified fuel according to the present invention can advantageously contain one or more biocidal agents, preferably in its aqueous phase.
  • Said biocidal agent is preferably a bactericide and/or a fungicide.
  • biocidal agents we may mention isothiazolones and their chlorinated derivatives, benzalkonium chlorides, organic peroxides, isothiocyanates, thiocyanates, ammonium salts, salts of amines, and oxazolidines.
  • the emulsified fuel can also contain at least one antigelling agent.
  • the following may be employed for example as antigelling agent: alcohols, glycols, derivatives of glycols or of alcohols, saline solutions.
  • additives constituted of one or more metallic or alkaline-earth catalysts that promote the reactions of post-combustion of soot.
  • the preferred catalysts are based on magnesium, calcium, barium, cerium, copper, iron or mixtures thereof. These catalytic promoters of soot destruction are easier to introduce in the emulsion than are generally compounds whose salts are soluble in water, and therefore in the aqueous phase of the emulsions according to the invention.
  • its sulfur content 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.
  • its sulfur content is preferably less than or equal to 1 wt. %, preferably less than or equal to 0.2 wt. %, and even more preferably less than or equal to 0.1 wt. %.
  • the content of polycyclic aromatic hydrocarbons of the fuel according to the invention is preferably less than or equal to 11 wt. %, more preferably less than or equal to 6 wt. %.
  • the emulsified fuel according to the invention preferably contains one or more other additives, which can be any additive usually employed in motor fuels, including for example but nonlimitatively:
  • cetane number improvers such as for example inorganic or organic nitrates, for example ammonium nitrate, alkyl nitrates in which the alkyl radical, linear or branched, saturated or unsaturated (preferably branched and saturated) contains from 3 to 20 and preferably from 5 to 15 carbon atoms (in particular 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 alkyl peroxides in which the alkyl radical, linear or branched, saturated or unsaturated (preferably branched and saturated) contains from 2 to 20 and preferably from 2 to 15 carbon atoms (for example tert.-butyl peroxide);
  • inorganic or organic nitrates for example ammonium nitrate
  • alkyl nitrates in which the alkyl
  • filterability additives such as for example the copolymers ethylene/vinyl acetate (EVA), ethylene/vinyl propionate (EVP), ethylene/vinyl ethanoate (EVE), ethylene/methyl methacrylate (EMMA), ethylene/alkyl fumarate;
  • EVA ethylene/vinyl acetate
  • EVE ethylene/vinyl propionate
  • EMMA ethylene/vinyl ethanoate
  • EMMA ethylene/methyl methacrylate
  • antifoaming additives such as for example polysiloxanes, oxyalkylated polysiloxanes, amides of fatty acids;
  • detergent and/or anticorrosion additives such as for example amines, succinimides, alkenyl succinimides, polyalkylamines, polyalkyl polyamines and polyetheramines;
  • lubricant or antiwear additives such as for example fatty acids and their ester or amide derivatives, mono- and polycyclic carboxylic acids and their ester or amide derivatives;
  • cloud point additives such as for example long-chain olefin/(meth)acrylic ester/maleimide terpolymers, derivatives of esters of fumaric or maleic acids;
  • antisedimentation additives such as for example the copolymers (meth)acrylic acid/alkyl (meth)acrylate amidated by a polyamine, the polyamine alkylene succinimides, the derivatives of phthalamic acid and double-chain aliphatic amine;
  • one or more polyfunctional additives for cold operation such as for example polymers based on olefin and alkenyl nitrate.
  • the invention also relates to a method of preparation of an emulsified fuel as described previously, by preparing an emulsion of hydrocarbons and water, in the presence of the emulsifying system and some or all of other possible additives. All the conventional ways of preparing emulsions can be employed for this purpose.
  • the emulsified fuel according to the present invention can be used in various applications. It can be used in particular as fuel for heat engines (notably gasoline or diesel engines), or for fuel cells. Its use as diesel engine fuel is particularly advantageous, in particular for the new diesel engines equipped with direct injection systems.
  • the fuel according to the invention can also be used as fuel for thermal machines such as for example industrial or domestic boilers, furnaces, turbines, generators.
  • a particularly advantageous use is as domestic fuel oil, i.e. as fuel for domestic boilers.
  • the invention also relates to a composition of emulsifying additives that can be used for example in emulsified water/hydrocarbons fuels in order to improve their high-temperature stability.
  • This additive composition comprises 15 wt. % of at least one fatty acid ester of (poly)oxyalkylated polyol, and of at least one member of the group comprising the esters of fatty acid and of sorbitan and the products of condensation of a succinic acid or anhydride with at least one amine, polyamine, fatty acid, (poly)oxyalkylated fatty acid, alcohol, (poly)oxyalkylated alcohol.
  • This additive composition preferably contains from 15 to 100 wt. % of at least one glycerol ester, and of at least one member of the group comprising sorbitan ester and the products of condensation of a succinic acid or anhydride with at least one amine, polyamine, fatty acid, (poly)oxyalkylated fatty acid, alcohol, (poly)oxyalkylated alcohol and the mixtures of these compounds.
  • it contains from 15 to 100 wt. % of at least one sorbitan ester combined with at least one polyol ester as described previously, in a weight ratio of sorbitan ester/polyol ester ranging from 20/80 to 80/20.
  • the weight ratio of sorbitan ester/polyol ester varies from 40/60 to 60/40 inclusive. Even more preferably, the amounts by weight of each of the two types of esters are roughly equal (45/55 to 55/45).
  • composition of emulsifying additives according to the invention also contains at least one alcohol containing from 3 to 22 carbon atoms, and preferably from 6 to 12 carbon atoms.
  • Said alcohol which is preferably a monohydric alcohol, may be linear or branched, saturated or unsaturated. It preferably contains at least one saturated branched alcohol.
  • the weight ratios of alcohol/polyol ester and alcohol/sorbitan ester are identical or different, and advantageously both are less than or equal to 1. Preferably, each of these ratios is between 0.2 and 1.
  • composition of emulsifying additives according to the invention can moreover comprise from 0 to 85 wt. % of at least one compound that is the product of condensation of a succinic acid or anhydride with at least one amine, polyamine, fatty acid, (poly)oxyalkylated fatty acid, alcohol, (poly)oxyalkylated alcohol and the mixtures of these compounds.
  • a succinic acid or anhydride is advantageously substituted by a hydrocarbon radical which is preferably a polymeric radical, for example a polyisobutyl radical.
  • said additive composition will contain from 15 to 85 wt. % of at least one polyol ester and from 85 to 15% of at least one condensation product. More preferably, it will comprise from 20 to 50 wt. % of at least one polyol ester and from 50 to 80% of at least one condensation product.
  • Said additive composition can also contain an alcohol as described previously.
  • the additive composition according to the invention can also contain one or more of the additives or agents as described previously as being suitable for incorporation in the emulsified fuel according to the invention, such as for example, but nonlimitatively, one or more other emulsifying agents, one or more biocidal agents, one or more antigelling agents, one or more antisoot agents, one or more cetane number improvers, one or more filterability additives, one or more antifoaming additives, one or more detergent and/or anticorrosion additives, one or more lubricant or antiwear additives, one or more cloud point additives, one or more antisedimentation additives, one or more polyfunctional additives for cold operation.
  • the additive composition contains at least one cetane number improver selected from the inorganic or organic nitrates (for example alkyl nitrates), organic peroxides and mixtures of these two types of compounds.
  • a particularly preferred additive composition contains at least four types of additives: at least one first ester, at least one second ester, at least one alcohol and/or one condensation product and at least one cetane number improver, each of these additives being as described previously.
  • the additive composition is in the form of a mixture of the additives described previously.
  • the additive composition is in the form of a “mother solution”, i.e. a concentrated solution of said additives in a suitable solvent.
  • Said solution is prepared by dissolving the emulsifying additives and any other additives and/or agents in the solvent.
  • Said solvent can be selected from the aromatic solvents (and notably the solvents based on aromatic or naphtheno-aromatic hydrocarbons, such as for example but nonlimitatively toluene, xylenes, diisopropylbenzene or alternatively a petroleum fraction rich in aromatic hydrocarbons), petroleum fractions (in particular naphthas, gasolines, kerosenes, distillates), mineral and/or synthetic oils.
  • the “mother solutions” can contain for example from 20 to 80 wt. % and preferably from 40 to 70 wt. % of additives and agents.
  • the invention finally relates to a method of improving the thermal stability of a water/liquid hydrocarbons emulsified fuel, by using a composition of emulsifying additives as described previously.
  • a conventional gas oil G is used, complying with standard EN 590.
  • This gas oil has the following characteristics:
  • emulsified fuels E1 and E2 were prepared by emulsifying 87.64 wt. % of said gas oil with 10 wt. % of water, in the presence of 1.86 wt. % of an emulsifying system S and 0.5 wt. % of a cetane number improver (2-ethylhexyl nitrate).
  • the emulsified fuel E1 complies with the prior art, and its emulsifying system S1 is made up of:
  • Fuel E2 complies with the invention, and its emulsifying system S2 is made up of:
  • the stability of the emulsified fuels E1 and E2 was determined at room temperature, in accordance with the stability test by centrifugation described in standard NF M 07-101.
  • the diagram given in FIG. 1 below shows the results obtained, as the degree of sedimentation of the fuel (i.e. separation of the emulsion into phases) as a function of the centrifugation time. The higher the degree of sedimentation, the lower the stability of the emulsion.
  • Fuels E1 and E2 were also submitted to a test of stability in storage at high temperature (75° C.). This test was carried out as follows: Put 450 ml of emulsion in a sealed 500-ml bottle. Put this bottle in a stove at 75° C. Then investigate the progressive phase separation by measuring the heights of the phases at time intervals of 24 h. The phase separation time is reached when the heights of the phases no longer vary with time (stationary state).
  • phase separation time i.e. the time after which the aqueous and organic phases of the emulsified fuel are completely separated.
  • the emulsified fuels according to the invention display markedly increased stability in high-temperature storage, while maintaining excellent room-temperature stability, better than that of the emulsified fuels known in the prior art.
  • the emulsified fuels were prepared by emulsifying 87.64 wt. % of gas oil G of Example 1 with 10 wt. % of water, in the presence of 1.86 wt. % of emulsifying system S and 0.5 wt. % of a cetane number improver (2-ethylhexyl nitrate).
  • Test 2 of Example 1 thermo stability at 75° C. was repeated, using emulsifying systems according to the invention, containing the following two esters:
  • ester A′ sorbitan sesquioleate
  • ester B′ colza oil ethoxylated at 10 mol ethylene oxide per mole of triglyceride.
  • the emulsified fuels were prepared by emulsifying 86 wt. % of gas oil G of Example 1 with 11.70 wt. % of water treated by osmosis, in the presence of 2 wt. % of emulsifying system S and 0.3 wt. % of a cetane number improver (2-ethylhexyl nitrate).
  • this example shows that it is possible, within the scope of the present invention, to vary both the chemical nature and the respective contents of the two esters, as a function of the results that one wishes to obtain and taking into account the available products, their costs and their compatibility with other additives that are likely to be incorporated in the emulsified fuel.
  • Emulsified fuels according to the invention were prepared starting from these additive compositions by emulsifying 85.4 to 86 wt. % (depending on the tests) of gas oil G of Example 1 with 11.7 wt. % of water, 2 to 2.6 wt. % (depending on the tests) of emulsifying system S and 0.3 wt. % of a cetane number improver (2-ethylhexyl nitrate).
  • the precise content of gas oil G in the emulsified fuel is adjusted, for each test, taking into account the amount of emulsifying system S.
  • the stability of these fuels was determined at room temperature (25° C.), using a test performed as follows: 100 ml of emulsion were put in a finely graduated Erlenmeyer flask. After the emulsion had been stored at 25° C. for 24 hours, the content by volume of sedimented phase in the emulsion (the sedimented phase was constituted of large drops of aqueous phase that separated from the emulsion and coalesced at the bottom of the vessel) was determined (by direct reading on the graduated flask).
  • compositions of emulsifying additives used in the respective fuels E8 and E9 which contain, in addition to the said first and second esters, 2-ethylhexanol display better resistance to sedimentation: on adding 0.4 wt. % of alcohol, it lowers the sedimentation of the emulsified fuel at 25° C. by 25%, and on adding 0.6 wt. % of alcohol, this phenomenon of sedimentation disappears completely.
  • Test 2 of Example 1 thermo stability at 75° C. was repeated, using emulsifying systems according to the invention, containing the following two surfactants:
  • ester B colza oil ethoxylated at 30 mol ethylene oxide per mole of triglyceride.
  • Surfactant C product of condensation of a polyisobutene succinic anhydride with a tetraethylenepentamine in a mass ratio amine to anhydride/amine of 1.2.
  • the emulsified fuels were prepared by emulsifying 86.75 wt. % of gas oil G of Example 1 with 11.70 wt. % of water treated by osmosis, in the presence of 1.25 wt. % of emulsifying system S and 0.3 wt. % of a cetane number improver (2-ethylhexyl nitrate).
  • this example shows that it is possible, within the scope of the present invention, to vary both the chemical nature and the respective contents of the two surfactants, as a function of the results that one wishes to obtain and taking into account the available products, their costs and their compatibility with other additives that are likely to be incorporated in the emulsified fuel.
  • Test 2 of Example 1 thermo stability at 75° C. was repeated, using emulsifying systems according to the invention, containing the following three surfactants:
  • ester A sorbitan monooleate
  • ester B colza oil ethoxylated at 30 mol ethylene oxide per mole of triglyceride.
  • Surfactant C product of condensation of a polyisobutene succinic anhydride with a tetraethylenepentamine in a mass ratio amine to anhydride/amine of 1.2.
  • the emulsified fuels were prepared by emulsifying 86.75 wt. % of gas oil G of Example 1 with 11.70 wt. % of water treated by osmosis, in the presence of 1.25 wt. % of emulsifying system S and 0.3 wt. % of a cetane number improver (2-ethylhexyl nitrate).
  • this example shows that it is possible, within the scope of the present invention, to vary both the chemical nature and the respective contents of the two esters, as a function of the results that one wishes to obtain and taking into account the available products, their costs and their compatibility with other additives that are likely to be incorporated in the emulsified fuel.
  • Emulsified fuels according to the invention were prepared starting from these additive compositions by emulsifying 85.4 to 86 wt. % (depending on the tests) of gas oil G of Example 1 with 11.7 wt. % of water, 2.5 wt. % (depending on the tests) of emulsifying system S and 0.3 wt. % of a cetane number improver (2-ethylhexyl nitrate). The exact content of gas oil G in the emulsified fuel was adjusted, for each test, taking into account the amount of emulsifying system S.
  • the stability of these fuels was determined at room temperature (25° C.), by means of a test performed as follows: 100 ml of emulsion is put in a finely graduated Erlenmeyer flask. After the emulsion had been stored at 25° C. for 24 hours, the content by volume of the sedimented phase in the emulsion (the sedimented phase being constituted of large drops of aqueous phase that separated from the emulsion and coalesced at the bottom of the vessel) was determined (by direct reading on the graduated flask).
  • the respective emulsifying systems S12 and S13 contain, in addition to the first stated; second esters and third surfactant, 2-ethylhexanol, display better resistance to sedimentation: on adding 28.5 wt. % of alcohol, the phenomenon of sedimentation disappears completely.
  • Test 2 of Example 1 thermo stability at 75° C. was repeated, using emulsifying systems according to the invention, containing the following two surfactants:
  • ester B′′ dioleate of polyethylene glycol 400 or polyalkoxylated ethylene glycol 400.
  • Surfactant C product of condensation of a succinic acid or anhydride with a polyamine.
  • the emulsified fuels were prepared by emulsifying 86.75 wt. % of gas oil G of Example 1 with 11.70 wt. % of water treated by osmosis, in the presence of 1.25 wt. % of emulsifying system S and 0.3 wt. % of a cetane number improver (2-ethylhexyl nitrate).
  • this example shows that it is possible, within the scope of the present invention, to vary both the chemical nature and the respective contents of the two surfactants, as a function of the results that one wishes to obtain and taking into account the available products, their costs and their compatibility with other additives that are likely to be incorporated in the emulsified fuel.

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  • Chemical & Material Sciences (AREA)
  • 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)
US10/525,328 2003-06-02 2004-06-01 Water/hydrocarbon emulsified fuel preparation and use thereof Abandoned US20060075680A1 (en)

Applications Claiming Priority (3)

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FR0306614A FR2855525B1 (fr) 2003-06-02 2003-06-02 Combustible emulsionne eau/hydrocarbures, sa preparation et ses utilisations
FR03/06614 2003-06-02
PCT/FR2004/001343 WO2004108864A2 (fr) 2003-06-02 2004-06-01 Combustible emulsionne eau / hydrocarbures, sa preparation et ses utilisations

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CN (1) CN1798825A (fr)
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007127059A3 (fr) * 2006-04-27 2008-02-07 H2Diesel Inc Composition de biocombustible et procédé de production d'un biocombustible
US20100087656A1 (en) * 2005-03-29 2010-04-08 Dries Muller Compositions Containing Fatty Acids and/or Derivatives Thereof and a Low Temperature Stabilizer
US20100275508A1 (en) * 2007-12-26 2010-11-04 Total Raffinage Marketing Bifunctional additives for liquid hydrocarbons obtained by grafting starting with copolymers of ethylene and/or propylene and vinyl ester
WO2011028183A1 (fr) * 2009-09-04 2011-03-10 Singapore Emulsion Fuel Pte Ltd Compositions d'additif pour carburant et leurs procédés de préparation, et carburant à émulsion les contenant
CN103074128A (zh) * 2013-01-24 2013-05-01 九峰能源科技（上海）有限公司 一种水/烃乳化燃料
WO2012135515A3 (fr) * 2011-03-29 2013-05-10 Fuelina, Inc. Combustible hydride et son procédé de fabrication
US20140318004A1 (en) * 2011-06-29 2014-10-30 Jens Mogens Nielsen Composition
US9109179B2 (en) 2012-04-20 2015-08-18 Broadleaf Energy, LLC Renewable biofuel
GB2538204A (en) * 2014-03-12 2016-11-09 Nielsen Co Us Llc Methods and apparatus to gather and analyze electroencephalographic data
US10308885B2 (en) 2014-12-03 2019-06-04 Drexel University Direct incorporation of natural gas into hydrocarbon liquid fuels
US11421168B2 (en) * 2017-12-27 2022-08-23 Bp Oil International Limited Methods for preparing fuel additives

Families Citing this family (3)

* Cited by examiner, † Cited by third party
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CN103923714A (zh) * 2013-01-10 2014-07-16 冯崇谦 纳米乳化清洁柴油
CN103468330B (zh) * 2013-09-22 2016-01-13 清华大学 一种内燃机用全馏分燃料及其应用
CN110105991B (zh) * 2019-06-18 2021-07-30 天津中安信业集团有限公司 一种用于汽油车辆减排节油的太赫兹水基燃油添加剂及其制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010005955A1 (en) * 1999-07-07 2001-07-05 Lubrizol Corporation, A Corporation Of The State Of Ohio Concentrated emulsion for making an aqueous hydrocarbon fuel

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU81921A1 (fr) * 1979-11-22 1981-06-04 Labofina Sa Compositions de carburant pour moteur diesel et procede pour les preparer
FR2746106B1 (fr) * 1996-03-15 1998-08-28 Combustible emulsionne et l'un de ses procedes d'obtention
AU774374B2 (en) * 2000-01-12 2004-06-24 Cam Tecnologie S.P.A. Fuel comprising an emulsion between water and a liquid hydrocarbon
ITMI20011002A1 (it) * 2001-05-16 2002-11-16 Ind Generali S P A Composizioni per carburanti ecologici procedimenti di preparazione e l'impego delle stesse
TW589369B (en) * 2001-07-11 2004-06-01 Kune-Muh Tsai Emulsion fuel oil additive
GB0124117D0 (en) * 2001-10-08 2001-11-28 Ici Plc Fuel emulsion

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010005955A1 (en) * 1999-07-07 2001-07-05 Lubrizol Corporation, A Corporation Of The State Of Ohio Concentrated emulsion for making an aqueous hydrocarbon fuel

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100087656A1 (en) * 2005-03-29 2010-04-08 Dries Muller Compositions Containing Fatty Acids and/or Derivatives Thereof and a Low Temperature Stabilizer
US9133409B2 (en) * 2005-03-29 2015-09-15 Arizona Chemical Company, Llc Compositions containing fatty acids and/or derivatives thereof and a low temperature stabilizer
WO2007127059A3 (fr) * 2006-04-27 2008-02-07 H2Diesel Inc Composition de biocombustible et procédé de production d'un biocombustible
US20100037513A1 (en) * 2006-04-27 2010-02-18 New Generation Biofuels, Inc. Biofuel Composition and Method of Producing a Biofuel
US20100275508A1 (en) * 2007-12-26 2010-11-04 Total Raffinage Marketing Bifunctional additives for liquid hydrocarbons obtained by grafting starting with copolymers of ethylene and/or propylene and vinyl ester
WO2011028183A1 (fr) * 2009-09-04 2011-03-10 Singapore Emulsion Fuel Pte Ltd Compositions d'additif pour carburant et leurs procédés de préparation, et carburant à émulsion les contenant
EP2865735A1 (fr) * 2011-03-29 2015-04-29 Fuelina, Inc. Carburant hybride et son procédé de fabrication
WO2012135515A3 (fr) * 2011-03-29 2013-05-10 Fuelina, Inc. Combustible hydride et son procédé de fabrication
US9493709B2 (en) 2011-03-29 2016-11-15 Fuelina Technologies, Llc Hybrid fuel and method of making the same
US20170009165A1 (en) * 2011-03-29 2017-01-12 Fuelina, Inc. Hybrid fuel and method of making the same
EP3354711A1 (fr) * 2011-03-29 2018-08-01 Fuelina Technologies, LLC Carburant hybride et son procédé de fabrication
US20140318004A1 (en) * 2011-06-29 2014-10-30 Jens Mogens Nielsen Composition
US9109179B2 (en) 2012-04-20 2015-08-18 Broadleaf Energy, LLC Renewable biofuel
CN103074128A (zh) * 2013-01-24 2013-05-01 九峰能源科技（上海）有限公司 一种水/烃乳化燃料
GB2538204A (en) * 2014-03-12 2016-11-09 Nielsen Co Us Llc Methods and apparatus to gather and analyze electroencephalographic data
GB2538204B (en) * 2014-03-12 2021-04-14 Nielsen Consumer Llc Methods and apparatus to gather and analyze electroencephalographic data
US10308885B2 (en) 2014-12-03 2019-06-04 Drexel University Direct incorporation of natural gas into hydrocarbon liquid fuels
US11421168B2 (en) * 2017-12-27 2022-08-23 Bp Oil International Limited Methods for preparing fuel additives

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FR2855525B1 (fr) 2005-07-08
BRPI0410865A (pt) 2006-07-04
CA2527324A1 (fr) 2004-12-16
FR2855525A1 (fr) 2004-12-03
WO2004108864A2 (fr) 2004-12-16
OA13176A (en) 2006-12-13
JP2006526680A (ja) 2006-11-24
EP1636326A2 (fr) 2006-03-22
CN1798825A (zh) 2006-07-05

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