EP0475620B1 - Microemulsion diesel fuel compositions and method of use - Google Patents
Microemulsion diesel fuel compositions and method of use Download PDFInfo
- Publication number
- EP0475620B1 EP0475620B1 EP91307780A EP91307780A EP0475620B1 EP 0475620 B1 EP0475620 B1 EP 0475620B1 EP 91307780 A EP91307780 A EP 91307780A EP 91307780 A EP91307780 A EP 91307780A EP 0475620 B1 EP0475620 B1 EP 0475620B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- surfactant
- diesel fuel
- microemulsion
- surfactants
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
-
- 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
-
- 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
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/12—Use of additives to fuels or fires for particular purposes for improving the cetane number
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B3/00—Engines characterised by air compression and subsequent fuel addition
- F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
Definitions
- microemulsion fuel compositions There is a wide variety of microemulsion fuel compositions known in the art. A disadvantage of these has been a lack of stability under conditions to which the fuels have been exposed. Prior compositions, for example, have been unstable and have tended to de-emulsify at high and at low temperatures; high temperature de-emulsification has been a special problem. Further, the addition of even very small amounts of salt as by exposure to salt-containing air or water has caused severe de-emulsification problems in prior formulations that did not contain alcohols. Another disadvantage of prior microemulsion fuel compositions has been the high concentrations of surfactants required to form the microemulsions. Prior inventions, generally, employed one or more parts of surfactant per part of solubilized water.
- EP-A-22110 there is disclosed an emulsifier system comprising (i) an alkylphenol ethylene oxide adduct nonionic surface active agent and (ii) a calcium dodecylbenzene sulphonate anionic surface active agent in a specified range of proportions.
- the system may be employed to manufacture aqueous emulsions of diesel oil. From 1 to 10 wt.% of water and 0.5 to 5 grams per litre of the emulsifier system may be employed.
- a diesel fuel composition which comprises:
- the said first and second surfactants are each selected only from said ethoxylated compounds
- the said amount of water present is from 2 to 20 wt.%, more especially from 2 to 15 wt.%
- the composition may also contain up to 30 wt.%, based on the weight of water present, of a C1 to C3 alkanol.
- the cetane improver additive is preferably selected from ammonium nitrate, ammonium nitrite, hydrogen peroxide, ammonium hypochlorite, ammonium chlorite, ammonium perchlorate, ammonium chlorate, perchloric acid, chlorous acid, hypochlorous acid, ammonium hypobromite, ammonium bromate, hypobromous acid, bromic acid, ammonium hypoiodite, ammonium periodate, hypoiodous acid, iodic acid, periodic acid, 2,4 dinitrophenyl hydrazine, 2,5 dinitrrophenol, 2,6 dinitrophenol, 2,4 dinitroresorcinol, nitroguanidine, 3 nitro-1,2,4-triazole, 2 nitro imidazole, 4 nitro imidazole, pricric acid, cumene hydroperoxide, cyanuric acid, nitroglycerin, nitrobenzene, trinitrotoluene, and mixtures thereof.
- At least one defined hydrophilic surfactant ((d)(i)) and at least one defined lipophilic surfactant ((d)(ii)) are selected and their ratio adjusted with respect to their combined hydrophilic and lipophilic properties such that they form with the fuel and the aqueous composition a single phase, translucent microemulsion.
- the said hydrophilic surfactant(s) is defined by a set of operations wherein a blend of equal volumes of fuel and aqueous composition with 2 grams of said surfactant per deciliter of liquids forms a lower phase microemulsion at 20°C such that the volume ratio of fuel (oil) to surfactant (Vo/Vs) in the microemulsion phase is at least 0.5, preferably greater than 1 and more preferably greater than 2.
- lower phase microemulsion is descriptive in context since it means that the aforementioned system consisting of the hydrophilic surfactant and equal volumes of fuel and aqueous composition separates into an aqueous lower phase containing most of the surfactant in equilibrium with an excess fuel (oil) phase which is essentially surfactant-free.
- Optional hydrophilic surfactants defined by the above properties include the alkyl carboxylic and alkylaryl sulfonic acid salts wherein the alkyl group is a C9 to C18 linear, branched or bilinear structure, the aryl group is selected from benzene, toluene, orthoxylene, and naphthalene, and the salt is a salt of an alkali metal, ammonia, or alkanol amine.
- Essential in the present invention are the ethoxylated C12-C18 alkyl ammonium salts of C9-C24 alkyl carboxylic and alkylaryl sulfonic acids containing 6 or more ethylene oxide (hereinafter EO) groups, wherein the alkyl and aryl groups are suitably as previously defined above.
- EO ethylene oxide
- hydrophilic alkyl carboxylic and alkylaryl sulfonic acid salts include monoethanol ammonium laurate, ammonium palmitate, diethanol ammonium stearate, monoethanol ammonium nonyl o-xylene sulfonate, sodium dodecyl benzene sulfonate, ammonium tetradecyl benzene sulfonate, diethanol ammonium hexadecyl benzene sulfonate, and sodium dodecyl naphthalene sulfonate.
- Preferred hydrophilic carboxylic acid salts include monoethanol ammonium oleate, penta-, deca-, and hexadeca-ethoxy octadecyl ammonium oleate.
- Preferred hydrophilic sulfonic acid salts include penta- and deca-ethoxy octadecyl ammonium benzene sulfonate (designated C12BS-E18-5 and C12BS-E18-10, respectively), heptaethoxy octadecyl ammonium dodecyl o-xylene sulfonate (designated C12XS-E18-7) and decaethoxy octadecyl ammonium dodecyl ortho xylene sulfonate (designated C12XS-E18-10).
- hydrophilic ethoxylated alkyl phenols include Igepal® DM 710, Igepal® DM 730, and Igepal® DM 880 available from GAF which are chemically dinonyl phenols ethoxylated with 15, 24, and 49 moles of EO, respectively.
- Igepal® DM 530 which is dinonyl phenol ethoxylated with 9 moles of ethylene oxide.
- ethoxylated alkyl phenols include Tritons® X100, X102, and X114 available from Rohm and Haas of Philadelphia, Pa., and Igepals® CO 610, 630, 660, 710, 720, 730, 850, and 880 which are chemically mono-octyl or nonyl phenols ethoxylated with from 8 to 30 EO.
- the said lipophilic surfactant for purposes of this invention is a surfactant having the properties of providing at 2 g/dl concentration in equal volumes of fuel and aqueous composition an upper phase microemulsion at 20°C such that the volume ratio of water to surfactant (Vw/Vs) in the microemulsion phase is at least 0.5, preferably greater than 1 and most preferably greater than 2.
- the term "upper phase" microemulsion as used in defining the lipophilic surfactant ingredient means that the system consisting of the surfactant in equal volumes of fuel and aqueous composition separates into a surfactant containing oil upper phase in equilibrium with an excess aqueous phase which is essentially surfactant free.
- the lipophile having been defined by the above properties includes ethoxylated alkyl phenols and alkyl and alkylaryl sulfonic acid salts wherein the alkyl group is a C12 to C24 linear, branched, or bilinear structure, the aryl group is selected from benzene, toluene, orthoxylene, and naphthalene; and the salt is a salt of an alkali metal, ammonia or alkanol amine.
- Essential in the present invention are the ethoxylated C12-C18 alkyl ammonium salts of C9-C24 alkyl carboxylic and alkylaryl sulfonic acids containing less than six EO groups, wherein the alkyl and aryl groups are suitably as previously defined above.
- optional lipophilic alkyl aryl sulfonates include monoethanol ammonium dodecyl o-xylene sulfonate, sodium tetradecyl o-xylene sulfonate, sodium hexadecyl o-xylene sulfonate, diethanol ammonium pentadecyl o-xylene sulfonate, triethanol ammonium octadecyl o-xylene sulfonate (prepared from penta and hexa propylene), sodium octapropylene benzene sulfonate, sodium tetracosyl toluene sulfonate, and various high molecular weight petroleum sulfonates.
- essential lipophilic surfactants are di-ethoxy octadecyl ammonium oleate, di- and penta-ethoxy octadecyl ammonium dodecyl o-xylene sulfonate (designated E18-2 oleate, C12XS-E18-2 and C12XS-E18-5, respectively).
- Representative optional lipophilic ethoxylated alkyl phenols include Igepals CO 210 and CO 430 which are nonyl phenols containing 1.5 and 4 moles of EO, respectively, and Tritons X15 and X35 which are octyl phenols containing 1 and 3 moles of EO, respectively.
- Preferred lipophilic/hydrophilic blends of ethoxylated alkyl ammonium salts of alkylaryl sulfonic acids include penta-ethoxy octadecyl ammonium dodecyl benzene sulfonate combined with hepta-ethoxy octadecyl ammonium dodecyl benzene sulfonate and di-ethoxy cocoa ammonium dodecyl o-xylene sulfonate with deca-ethoxy octadecyl ammonium dodecyl oxylene sulfonate.
- blend of penta-ethoxy octadecyl ammonium dodecyl o-xylene sulfonate with hepta or deca-ethoxy octadecyl ammonium dodecyl o-xylene sulfonate i.e., a blend of C12XS-E18-5 with C12XS-E18-10.
- weight percent of a cosurfactant is included in the surfactant blend to improve the solubility of the surfactant in the fuel and reduce the viscosity of the microemulsion diesel fuel composition.
- the cosurfactants are of the class of alkylene glycol monoalkyl ethers, C4 to C6 alkanols and mixtures thereof.
- Representative cosurfactants include ethers such as ethylene glycol monopropyl ether, methylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethyl glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol n-butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether and tripropylene glycol monomethyl ether, and alkanols which include straight and branched chain members such as butanol and pentanol. Of the alkanols, tertiary amyl alcohol (TAA) is preferred. Of the ethers, ethylene glycol monobutyl ether is preferred.
- TAA tertiary amyl alcohol
- ethers ethylene glycol monobutyl ether is preferred.
- the ratio of the surfactants may have to be readjusted for changes in phase behavior brought about by the addition of cosurfactant.
- the weight ratio of hydrophilic to lipophilic surfactants may have to be readjusted for changes in phase behavior brought about by different aqueous reagents and variations in their concentration. For example, an increase in the concentration of the aqueous reagent ammonium nitrate, requires an increase in the ratio of hydrophilic to lipophilic surfactants.
- changes in the composition of the fuel necessitate readjustment of the surfactant ratio. For example, a higher concentration of aromatics in the fuel requires an increase in the ratio of hydrophilic to lipophilic surfactants.
- a change in surfactant ratio is inadequate to compensate for a given change in the fuel or aqueous composition, choice of a more (or less) hydrophilic surfactant pair.
- Nos. I to IV are not examples of the invention, but are included as background material.
- Microemulsions were prepared as follows. The surfactants were weighed into a 16 x 125 mm flat bottom tube fitted with a teflon-lined cap. A total of 15 ml of diesel fuel and water were added. The tubes were shaken and heated -30 minutes to 1 hour at 60-70°C. They were then tumbled overnight to 2 days on an automated tumbler. Most systems, particularly those made with the alkyl benzene sulfonates, did not clear at room temperature after 2 days of tumbling. They could be made to clear in most cases by temperature cycling 2 or 3 times from 70°C to 0°C. On storage at room temperature, clarity improved with age for the systems containing the MEA soaps.
- the volume of oil solubilized per gm of surfactant (oil uptake) is greater than the most preferred design criterion for a hydrophilic surfactant of 2 ml oil/gm surfactant.
- the volume of water solubilized per gm of surfactant (water uptake) is greater than the most preferred design criterion for a lipophilic surfactant of 2 ml water/gm surfactant.
- the combination C12BS-MEA/C12BS E18-2 represents a hydrophile-lipophile surfactant couple and their combined hydrophilic and lipophilic properties are varied by adjusting the weight ratio of C12BS-MEA/C12BS E18-2.
- Table II presents phase data for the C12BS-MEA/C12BS E18-2 surfactant couple at various water to Maraven oil ratios and total surfactant concentrations. The data were generated as follows. The surfactant concentration was fixed at, for example, 2 g per deciliter of oil and water at a water/oil ratio of 5/95. The weight fraction of C12BS-MEA, the hydrophile in the surfactant couple was then varied in the range between 0.45 and 0.60.
- microemulsion at each weight fraction of C12BS-MEA was noted after equilibrium was reached.
- a change in microemulsion type indicated the approximate phase transition boundary between upper and single or single and lower phase microemulsions. These transition boundaries are noted in Table II.
- the procedure was repeated at 1.5 and 1.0 g/dl surfactant concentration and the approximate transition boundaries determined. Note that the data was developed on a series of individual equilibrated tubes, each containing the specific ratio of surfactants at the listed total surfactant concentration in water and oil at a 5/95 volume ratio. The single phase region lies between the upper and lower phase transition boundaries.
- phase boundaries coincide indicates the minimum surfactant concentration which will solubilize 5% water in Maraven diesel fuel; in this case, it takes somewhat more than 1 g/dl of surfactant to form a stable microemulsion.
- the proximity to the phase transition boundaries indicates that this will not be a clear system. In general, the clearest systems are found farthest from the transition boundaries, that is, in the center of the single phase region. The closer the transition boundaries, the hazier the systems located between them. Thus, maximum clarity at a given water concentration is attained at higher surfactant concentrations.
- Table II presents similar phase data for the C12BS-MEA/C12BS E18-2 surfactants holding the water/oil volume ratio fixed at 4/96.
- the single phase region has broadened and at 2 g/dl surfactant extends between 0.47 and 0 59 wt. fraction of C12BS-MEA compared with a range of 0.48 to 0.56 for the 5/95 water/oil system. Again the clearest systems are found in the center of the single phase region and since the 4/96 systems are farther from the phase transition boundaries than are the 5/95 systems, they are also clearer in comparison.
- the 4/96 water/oil systems form single phase microemulsions at surfactant concentrations somewhat below 1 g/dl. Again, these microemulsions are turbid because of their proximity to the phase transition boundaries.
- Table II illustrate the critical nature of selecting and balancing the hydrophile/lipophile surfactant blend for a given amount of water and surfactant.
- the data indicate that stable microemulsions can be prepared with up to 5% water with less than 1.5% surfactant.
- An increase in surfactant concentration permits a proportionate increase in the amount of water solubilized.
- the C12XS-MEA/C12XS E18-5 system though not as extensively investigated as the C12BS-MEA/C12BS E18-2 system described above, provides a similar phase behavior pattern.
- the C12XS-MEA is the hydrophile; its increasing weight fraction leads to lower phase microemulsions.
- Phase data obtained for three water/oil ratios at a surfactant concentration fixed at 1.5 g/dl are given in the following table.
- the single phase region which lies between the upper phase transition (UTB) and the lower phase transition boundary (LTB), broadens and clarity improves with decreased water/oil ratio.
- the clarity of microemulsions in the center of the single phase region is somewhat better than observed with the C12BS-MEA/C12BS E18-2 system.
- the rate of equilibration is faster with the C12XS-MEA/C12XS E18-5 system; less temperature cycling is required and clarity is obtained sooner on ambient storage after temperature cycling.
- concentrates were prepared by backing out oil and in some cases part of the water from the final composition. For example, the following concentrate was prepared:
- the surfactants were dissolved in the diesel oil at room temperature and the water added last.
- the mixture was turbid initially but slowly cleared with mild warming (-40°C) and stirring over a period of several hours to finally form a clear amber "solution.”
- This fluid concentrate when diluted by a factor of 10 instantly forms with little mixing a bright microemulsion containing 2 wt.% surfactant and 4% water.
- This microemulsion remains clear over the temperature range of -10°C (lower cloud point) to >70°C (upper cloud point) and is indefinitely stable at room temperature. It is not known at this time whether the turbidity below -10°C is due to phase separation in the microemulsion or wax precipitation from the diesel fuel.
- the above concentrates have a water/surfactant volume ratio of 2/1.
- the water/surfactant ratio in this package is 3/1.
- a quantity, 1.89 g of this concentrate when diluted with 8.2 g of diesel oil instantly forms a clear microemulsion containing 2% surfactant and 6% water.
- This microemulsion is not quite as bright as the microemulsion prepared with concentrate NB 1448376A due to the higher water content. Brightness may be improved with optimization of surfactant H/L ratio. This essay holds promise of achieving even higher water/surfactant ratios.
- Table III describes microemulsion phase behavior with varying surfactant hydrophile/lipophile (H/L) ratio and salinity.
- H/L ratio depends on the average degree of ethoxylation in the surfactant mixture and is varied by changing the weight ratio of ethoxylated surfactants.
- ME microemulsion
- An upper phase microemulsion (U) forms at low H/L ratio and high salinity as a phase-separated system where an oil-continuous microemulsion is in equilibrium with excess settled water.
- a lower phase microemulsion (L) forms at high H/L ratio and low salinity as a system where water-continuous microemulsion is in equilibrium with excess floating oil.
- a single phase microemulsion forms over a relatively narrow range of H/L ratios and salinity and is a relatively clear, thermodynamically stable dispersion containing all the components.
- NTU nephelometer turbidity units
- Table III shows that in order to prepare single phase microemulsions at higher salinity, the proportion of more highly ethoxylated surfactant must be increased.
- the ratio of C12XS E18-10/C12XS E18-5 increases from 1/1 to 2.3/1 as we go from 5% to 10% NH4NO3. This ratio lies in the middle of the single phase region and has the lowest haze. The haziest systems occur near the U ⁇ S and S ⁇ L phase transition boundaries.
- carboxylate surfactants do not add sulfur to the diesel fuel microemulsion composition.
- Sulfur-containing compounds in diesel fuel are environmentally undesirable since they may lead to sulfur oxides in the diesel exhaust.
- Some localities have established maximum sulfur levels in diesel fuels; California, for example, specifies no more than 500 ppm.
- Table IV show that oleate surfactants are effective in preparing single phase microemulsions of water and aqueous NH4NO3 in diesel fuel.
- the aqueous phase to surfactant ratio is 2.5:1 indicating that the instant ethoxylated alkyl ammonium oleate surfactants are efficient microemulsifiers when properly balanced.
Description
- There is a wide variety of microemulsion fuel compositions known in the art. A disadvantage of these has been a lack of stability under conditions to which the fuels have been exposed. Prior compositions, for example, have been unstable and have tended to de-emulsify at high and at low temperatures; high temperature de-emulsification has been a special problem. Further, the addition of even very small amounts of salt as by exposure to salt-containing air or water has caused severe de-emulsification problems in prior formulations that did not contain alcohols. Another disadvantage of prior microemulsion fuel compositions has been the high concentrations of surfactants required to form the microemulsions. Prior inventions, generally, employed one or more parts of surfactant per part of solubilized water.
- In EP-A-22110 there is disclosed an emulsifier system comprising (i) an alkylphenol ethylene oxide adduct nonionic surface active agent and (ii) a calcium dodecylbenzene sulphonate anionic surface active agent in a specified range of proportions. The system may be employed to manufacture aqueous emulsions of diesel oil. From 1 to 10 wt.% of water and 0.5 to 5 grams per litre of the emulsifier system may be employed.
- It is well-known in the art that dispersions of water and/or one or two carbon alkanols in diesel fuel reduce harmful diesel emissions such as smoke, soot, particulates, and NOx. It is also well-known that debits associated with water and alkanols in diesel fuels entail a severe reduction in cetane number and a marked ignition delay often requiring engine and/or operating parameter modification such as advanced ignition timing or the installation of glow plugs.
- It is an object of the present invention to provide a diesel fuel microemulsion (a) in which these debits are diminished or eliminated, (b) which still retains the advantage of emissions reduction and (c) which still has good stability.
- According to the present invention there is provided a diesel fuel composition which comprises:
- (a) a diesel fuel;
- (b) 1.0 to 30.0 weight percent of water based upon said diesel fuel;
- (c) a cetane number improver additive, present in an amount up to, but less than, 20.0 weight percent based upon said water, said additive being selected from an inorganic oxidizer, a polar organic oxidizer and a nitrogen oxide-containing compound; and
- (d) 0.5 to 15.0 wt.% based on the diesel fuel, of a surfactant system comprising
- (i) one or more first surfactants selected from surfactants capable of forming a lower phase microemulsion at 20°C when combined with equal volumes of the fuel and water at a concentration of 2 grams of surfactant per deciliter of fuel plus water, which microemulsion phase has a volume ratio of water to surfactant of at least 2; at least one said first surfactant being an ethoxylated C₁₂-C₁₈ alkyl ammonium salt of a C₉-C₂₄ alkyl carboxylic or alkylaryl sulfonic acid containing 6 or more ethylene oxide groups; and
- (ii) one or more second surfactants selected from surfactants capable of forming an upper phase microemulsion at 20°C when combined with equal volumes of the fuel and water at a concentration of 2 grams of surfactant per deciliter of fuel plus water, which microemulsion phase has a volume ratio of water to surfactant of at least 2; at least one said surfactant being an ethoxylated C₁₂-C₁₈ alkyl ammonium salt of a C₉-C₂₄ alkyl carboxylic or alkylaryl sulfonic acid containing less than 6 ethylene oxide groups;
- Preferably the said first and second surfactants are each selected only from said ethoxylated compounds
- Preferably the said amount of water present is from 2 to 20 wt.%, more especially from 2 to 15 wt.%
- The composition may also contain up to 30 wt.%, based on the weight of water present, of a C₁ to C₃ alkanol.
- The cetane improver additive is preferably selected from ammonium nitrate, ammonium nitrite, hydrogen peroxide, ammonium hypochlorite, ammonium chlorite, ammonium perchlorate, ammonium chlorate, perchloric acid, chlorous acid, hypochlorous acid, ammonium hypobromite, ammonium bromate, hypobromous acid, bromic acid, ammonium hypoiodite, ammonium periodate, hypoiodous acid, iodic acid, periodic acid, 2,4 dinitrophenyl hydrazine, 2,5 dinitrrophenol, 2,6 dinitrophenol, 2,4 dinitroresorcinol, nitroguanidine, 3 nitro-1,2,4-triazole, 2 nitro imidazole, 4 nitro imidazole, pricric acid, cumene hydroperoxide, cyanuric acid, nitroglycerin, nitrobenzene, trinitrotoluene, and mixtures thereof.
- In the practice of the present invention, at least one defined hydrophilic surfactant ((d)(i)) and at least one defined lipophilic surfactant ((d)(ii)) are selected and their ratio adjusted with respect to their combined hydrophilic and lipophilic properties such that they form with the fuel and the aqueous composition a single phase, translucent microemulsion. The said hydrophilic surfactant(s) is defined by a set of operations wherein a blend of equal volumes of fuel and aqueous composition with 2 grams of said surfactant per deciliter of liquids forms a lower phase microemulsion at 20°C such that the volume ratio of fuel (oil) to surfactant (Vo/Vs) in the microemulsion phase is at least 0.5, preferably greater than 1 and more preferably greater than 2. The term "lower phase" microemulsion is descriptive in context since it means that the aforementioned system consisting of the hydrophilic surfactant and equal volumes of fuel and aqueous composition separates into an aqueous lower phase containing most of the surfactant in equilibrium with an excess fuel (oil) phase which is essentially surfactant-free.
- Optional hydrophilic surfactants defined by the above properties include the alkyl carboxylic and alkylaryl sulfonic acid salts wherein the alkyl group is a C₉ to C₁₈ linear, branched or bilinear structure, the aryl group is selected from benzene, toluene, orthoxylene, and naphthalene, and the salt is a salt of an alkali metal, ammonia, or alkanol amine. Essential in the present invention are the ethoxylated C₁₂-C₁₈ alkyl ammonium salts of C₉-C₂₄ alkyl carboxylic and alkylaryl sulfonic acids containing 6 or more ethylene oxide (hereinafter EO) groups, wherein the alkyl and aryl groups are suitably as previously defined above.
- Representative examples of the optional hydrophilic alkyl carboxylic and alkylaryl sulfonic acid salts include monoethanol ammonium laurate, ammonium palmitate, diethanol ammonium stearate, monoethanol ammonium nonyl o-xylene sulfonate, sodium dodecyl benzene sulfonate, ammonium tetradecyl benzene sulfonate, diethanol ammonium hexadecyl benzene sulfonate, and sodium dodecyl naphthalene sulfonate. Preferred hydrophilic carboxylic acid salts include monoethanol ammonium oleate, penta-, deca-, and hexadeca-ethoxy octadecyl ammonium oleate. Preferred hydrophilic sulfonic acid salts include penta- and deca-ethoxy octadecyl ammonium benzene sulfonate (designated C₁₂BS-E18-5 and C₁₂BS-E18-10, respectively), heptaethoxy octadecyl ammonium dodecyl o-xylene sulfonate (designated C₁₂XS-E18-7) and decaethoxy octadecyl ammonium dodecyl ortho xylene sulfonate (designated C₁₂XS-E18-10). The ethoxylated alkyl amines used in preparing the ethoxylated alkyl ammonium salts of alkyl aryl sulfonic acids can be obtained from Exxon Chemical, Performance Products, Tomah Products.
- Representative hydrophilic ethoxylated alkyl phenols include Igepal® DM 710, Igepal® DM 730, and Igepal® DM 880 available from GAF which are chemically dinonyl phenols ethoxylated with 15, 24, and 49 moles of EO, respectively. Preferred is Igepal® DM 530 which is dinonyl phenol ethoxylated with 9 moles of ethylene oxide. Other suitable ethoxylated alkyl phenols include Tritons® X100, X102, and X114 available from Rohm and Haas of Philadelphia, Pa., and Igepals® CO 610, 630, 660, 710, 720, 730, 850, and 880 which are chemically mono-octyl or nonyl phenols ethoxylated with from 8 to 30 EO.
- The said lipophilic surfactant for purposes of this invention is a surfactant having the properties of providing at 2 g/dl concentration in equal volumes of fuel and aqueous composition an upper phase microemulsion at 20°C such that the volume ratio of water to surfactant (Vw/Vs) in the microemulsion phase is at least 0.5, preferably greater than 1 and most preferably greater than 2. The term "upper phase" microemulsion as used in defining the lipophilic surfactant ingredient means that the system consisting of the surfactant in equal volumes of fuel and aqueous composition separates into a surfactant containing oil upper phase in equilibrium with an excess aqueous phase which is essentially surfactant free.
- The lipophile having been defined by the above properties includes ethoxylated alkyl phenols and alkyl and alkylaryl sulfonic acid salts wherein the alkyl group is a C₁₂ to C₂₄ linear, branched, or bilinear structure, the aryl group is selected from benzene, toluene, orthoxylene, and naphthalene; and the salt is a salt of an alkali metal, ammonia or alkanol amine. Essential in the present invention are the ethoxylated C₁₂-C₁₈ alkyl ammonium salts of C₉-C₂₄ alkyl carboxylic and alkylaryl sulfonic acids containing less than six EO groups, wherein the alkyl and aryl groups are suitably as previously defined above.
- Representative examples of optional lipophilic alkyl aryl sulfonates include monoethanol ammonium dodecyl o-xylene sulfonate, sodium tetradecyl o-xylene sulfonate, sodium hexadecyl o-xylene sulfonate, diethanol ammonium pentadecyl o-xylene sulfonate, triethanol ammonium octadecyl o-xylene sulfonate (prepared from penta and hexa propylene), sodium octapropylene benzene sulfonate, sodium tetracosyl toluene sulfonate, and various high molecular weight petroleum sulfonates. Preferred are the sodium and monoethanol ammonium salts of dodecyl o-xylene sulfonic acid. Representative of essential lipophilic surfactants are di-ethoxy octadecyl ammonium oleate, di- and penta-ethoxy octadecyl ammonium dodecyl o-xylene sulfonate (designated E18-2 oleate, C₁₂XS-E18-2 and C₁₂XS-E18-5, respectively).
- Representative optional lipophilic ethoxylated alkyl phenols include Igepals CO 210 and CO 430 which are nonyl phenols containing 1.5 and 4 moles of EO, respectively, and Tritons X15 and X35 which are octyl phenols containing 1 and 3 moles of EO, respectively.
- Preferred lipophilic/hydrophilic blends of ethoxylated alkyl ammonium salts of alkylaryl sulfonic acids include penta-ethoxy octadecyl ammonium dodecyl benzene sulfonate combined with hepta-ethoxy octadecyl ammonium dodecyl benzene sulfonate and di-ethoxy cocoa ammonium dodecyl o-xylene sulfonate with deca-ethoxy octadecyl ammonium dodecyl oxylene sulfonate. Most preferred is the blend of penta-ethoxy octadecyl ammonium dodecyl o-xylene sulfonate with hepta or deca-ethoxy octadecyl ammonium dodecyl o-xylene sulfonate, i.e., a blend of C₁₂XS-E18-5 with C₁₂XS-E18-10.
- Under certain circumstances, up to 20, generally 2 to 10, weight percent of a cosurfactant is included in the surfactant blend to improve the solubility of the surfactant in the fuel and reduce the viscosity of the microemulsion diesel fuel composition. The cosurfactants are of the class of alkylene glycol monoalkyl ethers, C₄ to C₆ alkanols and mixtures thereof. Representative cosurfactants include ethers such as ethylene glycol monopropyl ether, methylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethyl glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol n-butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether and tripropylene glycol monomethyl ether, and alkanols which include straight and branched chain members such as butanol and pentanol. Of the alkanols, tertiary amyl alcohol (TAA) is preferred. Of the ethers, ethylene glycol monobutyl ether is preferred.
- It is understood that when using a cosurfactant, the ratio of the surfactants may have to be readjusted for changes in phase behavior brought about by the addition of cosurfactant. It is also understood that the weight ratio of hydrophilic to lipophilic surfactants may have to be readjusted for changes in phase behavior brought about by different aqueous reagents and variations in their concentration. For example, an increase in the concentration of the aqueous reagent ammonium nitrate, requires an increase in the ratio of hydrophilic to lipophilic surfactants. Likewise changes in the composition of the fuel necessitate readjustment of the surfactant ratio. For example, a higher concentration of aromatics in the fuel requires an increase in the ratio of hydrophilic to lipophilic surfactants. It is also understood that when a change in surfactant ratio is inadequate to compensate for a given change in the fuel or aqueous composition, choice of a more (or less) hydrophilic surfactant pair. These points will become clear from the following Examples.
- In the following Examples, Nos. I to IV are not examples of the invention, but are included as background material.
- One hundred grams of the alkyl carboxylic or alkyl aryl sulfonic acid is weighed into a wide mouth jar. An appropriate weight of the ethoxylated alkyl amine, as listed in Table I, is added and stirred vigorously while warm from the heat of neutralization. Properties, neutralization weights, and chemical suppliers are listed in Table I.
- Microemulsions were prepared as follows. The surfactants were weighed into a 16 x 125 mm flat bottom tube fitted with a teflon-lined cap. A total of 15 ml of diesel fuel and water were added. The tubes were shaken and heated -30 minutes to 1 hour at 60-70°C. They were then tumbled overnight to 2 days on an automated tumbler. Most systems, particularly those made with the alkyl benzene sulfonates, did not clear at room temperature after 2 days of tumbling. They could be made to clear in most cases by temperature cycling 2 or 3 times from 70°C to 0°C. On storage at room temperature, clarity improved with age for the systems containing the MEA soaps. Systems based solely on the C₁₂XS E18-n surfactants were found to be extremely temperature sensitive and to deteriorate with age. Often systems which were initially single phase and clear, phase separated on storage at room temperature. The assumed cause was laboratory temperature fluctuations coupled with the extreme temperature sensitivity of these systems. Because of poor storage stability, blends of only C₁₂XS E18-n surfactants were eliminated early on from further study. However, work with these surfactants did demonstrate that clear microemulsions could be prepared with 3 vol.% water and as little as 1 g/dl (∼1%) surfactant. Clear single phase systems containing 5% water stabilized by 2 g/dl of the C₁₂XS E18-n surfactants were also prepared. Blends of these C₁₂XS E18-n surfactants with surfactants based on MEA (e.g. C₁₂BS-MEA or C₁₂XS-MEA) gave good stability and are described below.
- A 2 gm/dl mixture of monoethanol ammonium dodecyl benzene sulfonate (hereafter C₁₂BS-MEA) with equal volumes of Maraven diesel fuel (oil) and water forms a lower phase microemulsion at 20°C. The volume of oil solubilized per gm of surfactant (oil uptake) is greater than the most preferred design criterion for a hydrophilic surfactant of 2 ml oil/gm surfactant. A 2 gm/dl mixture of di-ethoxy octadecyl ammonium dodecyl benzene sulfonate (hereafter C₁₂BS E18-2) with equal volumes of Maraven diesel fuel and water forms an upper phase microemulsion at 20°C. The volume of water solubilized per gm of surfactant (water uptake) is greater than the most preferred design criterion for a lipophilic surfactant of 2 ml water/gm surfactant.
- The combination C₁₂BS-MEA/C₁₂BS E18-2 represents a hydrophile-lipophile surfactant couple and their combined hydrophilic and lipophilic properties are varied by adjusting the weight ratio of C₁₂BS-MEA/C₁₂BS E18-2. Table II presents phase data for the C₁₂BS-MEA/C₁₂BS E18-2 surfactant couple at various water to Maraven oil ratios and total surfactant concentrations. The data were generated as follows. The surfactant concentration was fixed at, for example, 2 g per deciliter of oil and water at a water/oil ratio of 5/95. The weight fraction of C₁₂BS-MEA, the hydrophile in the surfactant couple was then varied in the range between 0.45 and 0.60. The type of microemulsion at each weight fraction of C₁₂BS-MEA was noted after equilibrium was reached. A change in microemulsion type indicated the approximate phase transition boundary between upper and single or single and lower phase microemulsions. These transition boundaries are noted in Table II. The procedure was repeated at 1.5 and 1.0 g/dl surfactant concentration and the approximate transition boundaries determined. Note that the data was developed on a series of individual equilibrated tubes, each containing the specific ratio of surfactants at the listed total surfactant concentration in water and oil at a 5/95 volume ratio. The single phase region lies between the upper and lower phase transition boundaries. The point where these phase boundaries coincide indicates the minimum surfactant concentration which will solubilize 5% water in Maraven diesel fuel; in this case, it takes somewhat more than 1 g/dl of surfactant to form a stable microemulsion. However, the proximity to the phase transition boundaries indicates that this will not be a clear system. In general, the clearest systems are found farthest from the transition boundaries, that is, in the center of the single phase region. The closer the transition boundaries, the hazier the systems located between them. Thus, maximum clarity at a given water concentration is attained at higher surfactant concentrations.
- Table II presents similar phase data for the C₁₂BS-MEA/C₁₂BS E18-2 surfactants holding the water/oil volume ratio fixed at 4/96. The single phase region has broadened and at 2 g/dl surfactant extends between 0.47 and 0 59 wt. fraction of C₁₂BS-MEA compared with a range of 0.48 to 0.56 for the 5/95 water/oil system. Again the clearest systems are found in the center of the single phase region and since the 4/96 systems are farther from the phase transition boundaries than are the 5/95 systems, they are also clearer in comparison. The 4/96 water/oil systems form single phase microemulsions at surfactant concentrations somewhat below 1 g/dl. Again, these microemulsions are turbid because of their proximity to the phase transition boundaries.
- The data in Table II reinforce the conclusion that higher surfactant/water ratios provide clearer microemulsions. The single phase region at a surfactant concentration of 2 g/dl for the 3/97 water/oil system extends between 0.46 and 0.60 wt. fraction C₁₂BS-MEA. Thus microemulsions in the center of this range are even farther from the transition boundaries and, therefore, clearer than those found with 5/95 or 4/96 water/oil systems. The 3/97 system forms single phase microemulsions at surfactant concentrations above 0.75 g/dl. Comparison with the 5/95 and 4/96 water/oil systems shows that for all these water/oil ratios, the minimum surfactant concentration for single phase microemulsions corresponds to a water/surfactant ratio of -4/1.
- The data in Table II illustrate the critical nature of selecting and balancing the hydrophile/lipophile surfactant blend for a given amount of water and surfactant. The data indicate that stable microemulsions can be prepared with up to 5% water with less than 1.5% surfactant. An increase in surfactant concentration permits a proportionate increase in the amount of water solubilized. These surfactants are more efficient than those found in the previous art.
- The C₁₂XS-MEA/C₁₂XS E18-5 system, though not as extensively investigated as the C₁₂BS-MEA/C₁₂BS E18-2 system described above, provides a similar phase behavior pattern. In this case, the C₁₂XS-MEA is the hydrophile; its increasing weight fraction leads to lower phase microemulsions. Phase data obtained for three water/oil ratios at a surfactant concentration fixed at 1.5 g/dl are given in the following table.
- As discussed previously, the single phase region, which lies between the upper phase transition (UTB) and the lower phase transition boundary (LTB), broadens and clarity improves with decreased water/oil ratio. The clarity of microemulsions in the center of the single phase region is somewhat better than observed with the C₁₂BS-MEA/C₁₂BS E18-2 system. In addition, the rate of equilibration is faster with the C₁₂XS-MEA/C₁₂XS E18-5 system; less temperature cycling is required and clarity is obtained sooner on ambient storage after temperature cycling.
- In order to check whether other compositional paths to the final microemulsion might speed equilibration, we explored the use of concentrates as intermediate compositions. These concentrates were prepared by backing out oil and in some cases part of the water from the final composition. For example, the following concentrate was prepared:
- The surfactants were dissolved in diesel oil at room temperature and the water mixed in last. The system forms a thin, clear gel at room temperature which melts into a clear fluid on gentle warming. If 1.2 g of this concentrate is added to 14.1 ml of diesel fuel, the resulting mixture is turbid and clears slowly over a period of several hours to form a bright microemulsion. If the diesel fuel is mixed in stages with the concentrate over a period of several minutes, the final system is a clear microemulsion. This shows that equilibration rate depends on composition path as well as temperature path. It also suggests that it would be advantageous to predilute the above concentrate with some added diesel oil. With this in mind we prepared the following concentrate:
- The surfactants were dissolved in the diesel oil at room temperature and the water added last. The mixture was turbid initially but slowly cleared with mild warming (-40°C) and stirring over a period of several hours to finally form a clear amber "solution." This fluid concentrate when diluted by a factor of 10 instantly forms with little mixing a bright microemulsion containing 2 wt.% surfactant and 4% water. This microemulsion remains clear over the temperature range of -10°C (lower cloud point) to >70°C (upper cloud point) and is indefinitely stable at room temperature. It is not known at this time whether the turbidity below -10°C is due to phase separation in the microemulsion or wax precipitation from the diesel fuel.
- The above concentrates have a water/surfactant volume ratio of 2/1. In an attempt to raise the water/surfactant ratio, the following concentrate was prepared:
The water/surfactant ratio in this package is 3/1. No attempt was made to optimize the surfactant H/L ratio for the added water. Clarity was achieved by adjusting the oil/water ratio in the package. A quantity, 1.89 g of this concentrate when diluted with 8.2 g of diesel oil instantly forms a clear microemulsion containing 2% surfactant and 6% water. This microemulsion is not quite as bright as the microemulsion prepared with concentrate NB 1448376A due to the higher water content. Brightness may be improved with optimization of surfactant H/L ratio. This essay holds promise of achieving even higher water/surfactant ratios. - In order to determine whether the loss in cetane number due to microemulsified water could be eliminated by the addition of potential cetane improvers, we initiated experiments designed to incorporate NH₄NO₃ into the microemulsified aqueous phase. Table III describes the results of our studies to incorporate up to 10 wt.% NH₄NO₃ based on water. Since the microemulsions contain 10% aqueous phase, 10% NH₄NO₃ based on water translates into a 1% NH₄NO₃ concentration overall. Based on previous results with oil-soluble cetane improvers such as octyl nitrate, 0.1% or 1000 ppm NH₄NO₃ was thought to be an effective level for cetane improvement.
- Table III describes microemulsion phase behavior with varying surfactant hydrophile/lipophile (H/L) ratio and salinity. H/L ratio depends on the average degree of ethoxylation in the surfactant mixture and is varied by changing the weight ratio of ethoxylated surfactants. Listed under the column heading microemulsion (ME) type is the phase separation characteristic of a given composition. An upper phase microemulsion (U) forms at low H/L ratio and high salinity as a phase-separated system where an oil-continuous microemulsion is in equilibrium with excess settled water. A lower phase microemulsion (L) forms at high H/L ratio and low salinity as a system where water-continuous microemulsion is in equilibrium with excess floating oil. A single phase microemulsion (S) forms over a relatively narrow range of H/L ratios and salinity and is a relatively clear, thermodynamically stable dispersion containing all the components. The last column lists the nephelometer turbidity units (NTU), which are a measure of single phase microemulsion clarity. Below -50 NTU the system looks quite bright. From ∼50 to 100 NTU the system is clear but with very slight haze developing. From 100 to 200 NTU haze visibly increases but the microemulsion remains transparent. Above 200 NTU the system becomes more and more cloudy though it remains translucent. Readings below 150 NTU are considered satisfactory.
- Table III shows that in order to prepare single phase microemulsions at higher salinity, the proportion of more highly ethoxylated surfactant must be increased. Thus the ratio of C₁₂XS E18-10/C₁₂XS E18-5 increases from 1/1 to 2.3/1 as we go from 5% to 10% NH₄NO₃. This ratio lies in the middle of the single phase region and has the lowest haze. The haziest systems occur near the U → S and S → L phase transition boundaries.
-
- The advantage for carboxylate surfactants is that they do not add sulfur to the diesel fuel microemulsion composition. Sulfur-containing compounds in diesel fuel are environmentally undesirable since they may lead to sulfur oxides in the diesel exhaust. Some localities have established maximum sulfur levels in diesel fuels; California, for example, specifies no more than 500 ppm. The examples in Table IV show that oleate surfactants are effective in preparing single phase microemulsions of water and aqueous NH₄NO₃ in diesel fuel. The aqueous phase to surfactant ratio is 2.5:1 indicating that the instant ethoxylated alkyl ammonium oleate surfactants are efficient microemulsifiers when properly balanced. As in the case with the ethoxylated alkyl ammonium alkyl aryl sulfonates, increasing ethoxylation is required to balance the surfactants when using higher NH₄NO₃ concentrations. This shows the criticality of surfactant balancing which depends strongly on aqueous phase composition. Temperature sensitivity is again minimized by blending two or more surfactants with opposing temperature dependencies; MEA-oleate becomes more hydrophilic while the ethoxylated alkyl ammonium oleate become more lipophilic with increasing temperature. Blends of these surfactants give temperature insensitive microemulsions.
Claims (6)
- A diesel fuel composition which comprises:(a) a diesel fuel;(b) 1.0 to 30.0 weight percent of water based upon said diesel fuel;(c) a cetane number improver additive, present in an amount up to, but less than, 20.0 weight percent based upon said water, said additive being selected from an inorganic oxidizer, a polar organic oxidizer and a nitrogen oxide-containing compound; and(d) 0.5 to 15.0 wt% based on the diesel fuel, of a surfactant system comprising(i) one or more first surfactants selected from surfactants capable of forming a lower phase microemulsion at 20°C when combined with equal volumes of the fuel and water at a concentration of 2 grams of surfactant per deciliter of fuel plus water, which microemulsion phase has a volume ratio of water to surfactant of at least 2; at least one said first surfactant being an ethoxylated C₁₂-C₁₈ alkyl ammonium salt of a C₉-C₂₄ alkyl carboxylic or alkylaryl sulfonic acid containing 6 or more ethylene oxide groups; and(ii) one or more second surfactants selected from surfactants capable of forming an upper phase microemulsion at 20°C when combined with equal volumes of the fuel and water at a concentration of 2 grams of surfactant per deciliter of fuel plus water, which microemulsion phase has a volume ratio of water to surfactant of at least 2; at least one said surfactant being an ethoxylated C₁₂-C₁₈ alkyl ammonium salt of a C₉-C₂₄ alkyl carboxylic or alkylaryl sulfonic acid containing less the 6 ethylene oxide groups;the said first and second surfactants being present in a weight ratio which forms with components (a), (b) and (c) a single phase translucent microemulsion.
- A fuel composition as claimed in claim 1, wherein the said first and second surfactants are each selected only from said ethoxylated compounds.
- A diesel fuel composition according to either preceding claim, further including up to 20, preferably 2 to 10, weight percent based upon said diesel fuel, of a cosurfactant selected from alkylene glycol monoalkylethers and C₄ to C₆ alkanols and mixtures thereof.
- A diesel fuel composition according to any preceding claim, wherein said additive (c) is an ammonium compound selected from nitrate, nitrite, hypochlorite, chlorite, chlorate, perchlorate, hypobromite, bromate, hypoiodite and periodate.
- A diesel fuel composition according to any of claims 1 to 3, wherein said additive (c) is hydrogen peroxide or an acid selected from perchloric, chlorous, hypochlorous, cyanuric, hypobromous, bromic, hypoiodous, iodic and periodic.
- A diesel fuel composition according to any preceding claim, further containing an amount of up to 30 weight percent, based on the weight of water, of a C₁ to C₃ alkanol.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US57848390A | 1990-09-07 | 1990-09-07 | |
US57848290A | 1990-09-07 | 1990-09-07 | |
US578483 | 1990-09-07 | ||
US578482 | 1990-09-07 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0475620A2 EP0475620A2 (en) | 1992-03-18 |
EP0475620A3 EP0475620A3 (en) | 1992-07-22 |
EP0475620B1 true EP0475620B1 (en) | 1995-11-08 |
Family
ID=27077508
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91307780A Expired - Lifetime EP0475620B1 (en) | 1990-09-07 | 1991-08-23 | Microemulsion diesel fuel compositions and method of use |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0475620B1 (en) |
JP (1) | JP2974466B2 (en) |
CA (1) | CA2048906C (en) |
DE (1) | DE69114422T2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6858046B2 (en) | 1998-09-14 | 2005-02-22 | The Lubrizol Corporation | Emulsified water-blended fuel compositions |
CN101940981A (en) * | 2010-08-07 | 2011-01-12 | 武贵丙 | Highly watered micro-emulsified diesel oil additive, preparation method and application thereof |
US9303223B2 (en) | 2006-09-05 | 2016-04-05 | Cerion, Llc | Method of making cerium oxide nanoparticles |
Families Citing this family (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5584894A (en) * | 1992-07-22 | 1996-12-17 | Platinum Plus, Inc. | Reduction of nitrogen oxides emissions from vehicular diesel engines |
USRE35237E (en) * | 1989-11-22 | 1996-05-14 | Gunnerman Rudolf W | Aqueous fuel for internal combustion engine and method of combustion |
US5743922A (en) * | 1992-07-22 | 1998-04-28 | Nalco Fuel Tech | Enhanced lubricity diesel fuel emulsions for reduction of nitrogen oxides |
EP0682101A1 (en) * | 1994-03-17 | 1995-11-15 | Gerhard Auer | Water-fuel emulsion for combustion engines |
US6302929B1 (en) | 1994-04-04 | 2001-10-16 | Rudolf W. Gunnerman | Aqueous fuel for internal combustion engine and method of preparing |
US5669938A (en) * | 1995-12-21 | 1997-09-23 | Ethyl Corporation | Emulsion diesel fuel composition with reduced emissions |
HU216371B (en) * | 1996-09-23 | 1999-06-28 | Levente Fülöp | Stable macromolecular disperse fuel composition containing water for the operation of internal combustion engines ashybrid engines and process to produce said composition |
US5800576A (en) * | 1996-11-13 | 1998-09-01 | Quantum Energy Technologies Corporation | Water clusters and uses therefor |
US5997590A (en) * | 1996-11-13 | 1999-12-07 | Quantum Energy Technologies Corp. | Stabilized water nanocluster-fuel emulsions designed through quantum chemistry |
US6656236B1 (en) | 1997-12-12 | 2003-12-02 | Clean Fuel Technology, Inc. | Constant heating value aqueous fuel mixture and method for formulating the same |
CA2313686C (en) * | 1997-12-12 | 2011-02-22 | Caterpillar Inc. | Constant heating value aqueous fuel mixture and method for formulating the same |
WO2001018154A1 (en) * | 1999-09-06 | 2001-03-15 | Agrofuel Ab | Motor fuel for diesel engines |
ATE337388T1 (en) | 2000-01-12 | 2006-09-15 | Pirelli & C Ambiente Eco Techn | FUEL CONTAINING WATER-LIQUID HYDROCARBON EMULSION |
US6606856B1 (en) | 2000-03-03 | 2003-08-19 | The Lubrizol Corporation | Process for reducing pollutants from the exhaust of a diesel engine |
US7276093B1 (en) * | 2000-05-05 | 2007-10-02 | Inievep, S.A. | Water in hydrocarbon emulsion useful as low emission fuel and method for forming same |
US20030084658A1 (en) | 2000-06-20 | 2003-05-08 | Brown Kevin F | Process for reducing pollutants from the exhaust of a diesel engine using a water diesel fuel in combination with exhaust after-treatments |
SE523228C2 (en) | 2000-12-15 | 2004-04-06 | Akzo Nobel Nv | Fuel composition containing a hydrocarbon fraction, ethanol and an additive with water solubilizing capacity |
US7041145B2 (en) | 2001-07-09 | 2006-05-09 | Cam Technologie S.P.A. | Fuel comprising an emulsion between water and a liquid hydrocarbon |
US8511259B2 (en) | 2002-03-28 | 2013-08-20 | Cam Technologie S.P.A. | Method for reducing emission of pollutants from an internal combusion engine, and fuel emulsion comprising water and a liquid hydrocarbon |
US7413583B2 (en) | 2003-08-22 | 2008-08-19 | The Lubrizol Corporation | Emulsified fuels and engine oil synergy |
WO2008030813A1 (en) | 2006-09-05 | 2008-03-13 | Cerion Technology, Inc. | Method of conditioning an internal combustion engine |
US10435639B2 (en) | 2006-09-05 | 2019-10-08 | Cerion, Llc | Fuel additive containing lattice engineered cerium dioxide nanoparticles |
US7915470B2 (en) | 2006-09-08 | 2011-03-29 | Board Of Regents, The University Of Texas System | Coupled electrochemical method for reduction of polyols to hydrocarbons |
US20140041286A1 (en) * | 2007-09-24 | 2014-02-13 | Sylvatex, Inc. | Method of formulating a fuel composition for use in internal-combustion engines |
EP2253692A1 (en) | 2009-05-19 | 2010-11-24 | Universität zu Köln | Bio-hydrofuel compounds |
DE102009048223A1 (en) | 2009-10-05 | 2011-06-16 | Fachhochschule Trier | Process for the in-situ production of fuel-water mixtures in internal combustion engines |
DE202011107729U1 (en) | 2011-11-11 | 2012-01-12 | Elmar Vitt | Production and stabilization of water-oil emulsions by electro-osmosis |
ITRM20110694A1 (en) | 2011-12-29 | 2013-06-30 | Fuel S A E | STABILIZED EMULSIONS WITH WATER-EFFECTIVE DIESEL OIL. |
US10143661B2 (en) | 2013-10-17 | 2018-12-04 | Cerion, Llc | Malic acid stabilized nanoceria particles |
DE102014225815A1 (en) | 2014-12-15 | 2016-06-16 | Fachhochschule Trier | In-situ production of fuel-water mixtures in internal combustion engines |
DE202015003014U1 (en) | 2015-04-26 | 2015-05-28 | Elmar Vitt | Device for the indirect use of water-oil emulsions in vehicles and other external users |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1088759B (en) * | 1957-11-29 | 1960-09-08 | Exxon Research Engineering Co | Fuel for engines with compression ignition |
SE447392B (en) * | 1979-06-29 | 1986-11-10 | Berol Kemi Ab | EMULSION OF THE WATER IN A MINERAL OIL AND THE EMERGENCY |
US4477258A (en) * | 1980-10-30 | 1984-10-16 | Labofina, S.A. | Diesel fuel compositions and process for their production |
DE3525124A1 (en) * | 1985-07-13 | 1987-01-15 | Huels Chemische Werke Ag | FUELS AND HEATING OILS AND USE OF AN EMULGATOR SYSTEM FOR THE PRODUCTION OF THESE FUELS AND HEATING OILS |
-
1991
- 1991-08-09 CA CA002048906A patent/CA2048906C/en not_active Expired - Fee Related
- 1991-08-23 DE DE69114422T patent/DE69114422T2/en not_active Expired - Fee Related
- 1991-08-23 EP EP91307780A patent/EP0475620B1/en not_active Expired - Lifetime
- 1991-09-06 JP JP3227280A patent/JP2974466B2/en not_active Expired - Fee Related
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6858046B2 (en) | 1998-09-14 | 2005-02-22 | The Lubrizol Corporation | Emulsified water-blended fuel compositions |
US9303223B2 (en) | 2006-09-05 | 2016-04-05 | Cerion, Llc | Method of making cerium oxide nanoparticles |
US9340738B2 (en) | 2006-09-05 | 2016-05-17 | Cerion, Llc | Method of making cerium oxide nanoparticles |
CN101940981A (en) * | 2010-08-07 | 2011-01-12 | 武贵丙 | Highly watered micro-emulsified diesel oil additive, preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CA2048906A1 (en) | 1992-03-08 |
JPH04234492A (en) | 1992-08-24 |
EP0475620A2 (en) | 1992-03-18 |
CA2048906C (en) | 2002-12-10 |
EP0475620A3 (en) | 1992-07-22 |
DE69114422D1 (en) | 1995-12-14 |
DE69114422T2 (en) | 1996-03-21 |
JP2974466B2 (en) | 1999-11-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0475620B1 (en) | Microemulsion diesel fuel compositions and method of use | |
US4565548A (en) | Motor fuel composition | |
US4744796A (en) | Microemulsion fuel system | |
US4477258A (en) | Diesel fuel compositions and process for their production | |
US4561861A (en) | Motor fuel composition | |
US4392865A (en) | Hydrocarbon-water fuels, emulsions, slurries and other particulate mixtures | |
US4108193A (en) | Pipeline method for transporting viscous hydrocarbons | |
US4083698A (en) | Clear and stable liquid fuel compositions for internal combustion engines | |
EP0022110A1 (en) | Emulsifier and its use for the manufacture of an emulsion in mineral oil | |
KR20080034509A (en) | Multi-phase distillate fuel, compositions and concentrates containing emulsified boric acid | |
RU1831495C (en) | Fuel composition of microemulsion | |
US4764285A (en) | Oil spill microemulsion dispersants | |
EP0383522B1 (en) | Separation technique for oil ontaminated sludge | |
US4465494A (en) | Microemulsion of water in a liquid fuel | |
US7887604B1 (en) | Microemulsion (nanotechnology) fuel additive composition | |
US4534411A (en) | Micellar slug for oil recovery | |
EP0049921B1 (en) | Clear liquid fuel mixture for combustion engines | |
GB2066288A (en) | Diesel fuel compositions and process for their production | |
GB2336120A (en) | Solubilising water and fuel oil | |
EP0121964B1 (en) | Process for preparing an alkyl aryl sulphonate concentrate composition | |
US4502926A (en) | Method for electroplating metals using microemulsion additive compositions | |
GB2101628A (en) | Improved fuel comprising hydrocarbons containing alcohol | |
CN103421557B (en) | A kind of multifunctional fuel oil additive | |
WO1999044732A1 (en) | A composition for mixing oil and water to form a solution | |
GB2259518A (en) | Cleaning composition for use in seawater |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): BE DE FR GB IT NL |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): BE DE FR GB IT NL |
|
17P | Request for examination filed |
Effective date: 19930107 |
|
17Q | First examination report despatched |
Effective date: 19930723 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE FR GB IT NL |
|
REF | Corresponds to: |
Ref document number: 69114422 Country of ref document: DE Date of ref document: 19951214 |
|
ET | Fr: translation filed | ||
ITF | It: translation for a ep patent filed |
Owner name: MODIANO & ASSOCIATI S.R.L. |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19990625 Year of fee payment: 9 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010301 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20010301 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
NLXE | Nl: other communications concerning ep-patents (part 3 heading xe) |
Free format text: A REQUEST FOR RESTORATION TO THE PRIOR STATE (ART. 23 OF THE PATENTS ACT 1995) HAS BEEN FILED ON 23.11.01. |
|
NLXE | Nl: other communications concerning ep-patents (part 3 heading xe) |
Free format text: THE REQUEST FOR RESTORATION TO THE PRIOR STATE AS PROVIDED FOR IN ARTICLE 23 OF THE PATENTS ACT 1995 (SEE PUBLICATION IN HEADING XE OF THE PATENT BULLETIN OF 01.02.2002/02) HAS BEEN REJECTED. |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20040707 Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20040804 Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20040831 Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20040901 Year of fee payment: 14 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050823 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050823 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050831 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060301 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20050823 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060428 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20060428 |
|
BERE | Be: lapsed |
Owner name: *EXXON RESEARCH AND ENGINEERING CY Effective date: 20050831 |