CN105238468B - Kerosene micro-emulsion and preparation method thereof - Google Patents
Kerosene micro-emulsion and preparation method thereof Download PDFInfo
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- CN105238468B CN105238468B CN201510749329.2A CN201510749329A CN105238468B CN 105238468 B CN105238468 B CN 105238468B CN 201510749329 A CN201510749329 A CN 201510749329A CN 105238468 B CN105238468 B CN 105238468B
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Abstract
The invention discloses a kerosene micro-emulsion. The kerosene micro-emulsion is prepared from kerosene, a surfactant, a cosurfactant and water, wherein the cosurfactant is an alpha-amino acid and concretely is a glycine and phenylalanine mixture, and the surfactant is cetyltrimethylammonium bromide. The invention also provides a preparation method of the kerosene micro-emulsion. The kerosene micro-emulsion prepared in the invention has the advantages of clarified and transparent appearance, good stability, high water content, good combustion performance, small particle size, no layering at room temperature, a high temperature or a low temperature, no metal ions, sulfur element or other substances detrimental to environment, facilitation of complete combustion, and improvement of the combustion efficiency. The preparation method makes an oil-water mixed adsorption film generate ultralow interface tension in order to obtain the good kerosene micro-emulsion.
Description
Technical field
The present invention relates to microemulsion field, and in particular to a kind of Kerosene Microemulsified liquid and preparation method thereof.
Background technology
Microemulsion is a kind of thermodynamic stable system, generally by surfactant, cosurfactant, water phase and oil phase group
Into, particle diameter in the range of 10~100nm, there is appearance transparent, good stability, easily prepared, in material science, organic
The aspects such as chemistry, bioengineering, medical science cause increasing concern.Kerosene is as a kind of fuel source, inflammable and explosive, right
Kerosene carries out the safety effect that microemulsified can play anti-explosion explosion-suppression, while improve can kerosene burning more abundant, efficiency of combustion.By
Produce after water vapour expanded by heating when oil, water form W/O or O/W emulsions under Action of Surfactant in heating burning micro-
It is quick-fried so that the burning of kerosene secondary-atomizing more fully, greatly reduces the content of pernicious gas in waste gas.
Alcohol is the most frequently used cosurfactant.However, in the preparation of Kerosene Microemulsified liquid, due to methyl alcohol, ethanol, positive fourth
When alcohol is cosurfactant, water-soluble strong, the alcohol molecule being distributed in water phase is more, promotes surfactant molecule in water
Dissolving in phase, the surfactant being assigned on interface are less, are hardly formed Kerosene Microemulsified liquid, in addition with the increasing of carbochain
Plus, the volume of alcohol molecule increases successively, the resistance increase of its embedded interfacial film, reduces the flexible of interfacial film, rigidity reinforced, no
Beneficial to the bending of interfacial film, it is less useful for forming microemulsion, easily generates liquid crystalline phase.Therefore, find and a kind of new help surface
Activating agent, is developed the microemulsion fuel being close to raw coal oil that a kind of surface area is big, interfacial tension is low, solubilising power is strong and is become and ground
Study carefully focus.
The content of the invention
It is an object of the invention to solve at least the above and/or defect, and provide at least will be described later excellent
Point.
It is a still further object of the present invention to provide a kind of Kerosene Microemulsified liquid, which has good stability, water content height, flammability
The good, particle diameter of energy is little, room temperature is placed without the advantages of layering.
It is a still further object of the present invention to provide a kind of preparation method of Kerosene Microemulsified liquid, produces oil mixing with water adsorbed film
Ultralow interfacial tension, to obtain more preferable Kerosene Microemulsified liquid.
In order to realize these purposes of the invention and further advantage, there is provided a kind of Kerosene Microemulsified liquid, by kerosene, table
Face activating agent, cosurfactant and water are made, wherein, one or more for a-amino acid of the cosurfactant.
Preferably, described Kerosene Microemulsified liquid, the a-amino acid are the mixture of glycine and phenylalanine.
Preferably, described Kerosene Microemulsified liquid, the surfactant are cetyl trimethylammonium bromide.
Preferably, described Kerosene Microemulsified liquid, is prepared from the following raw materials in parts by weight:300~500 parts of kerosene, 100
The mixture of~300 parts of cetyl trimethylammonium bromides, 0.6~1 part of glycine and phenylalanine, 198~200 parts of water systems
Into.
Preferably, described Kerosene Microemulsified liquid, is prepared from the following raw materials in parts by weight:400 parts of kerosene, 200 part ten
The mixture of six alkyl trimethyl ammonium bromides, 0.8 part of glycine and phenylalanine, 199.2 parts of water are made.
A kind of preparation method of described Kerosene Microemulsified liquid, comprises the following steps:
Step one, cetyl trimethylammonium bromide is added by above-mentioned parts by weight in kerosene, obtain the first mixture;
Step 2, glycine and phenylalanine is added in water by above-mentioned parts by weight, obtain the second mixture;
Step 3, by first mixture and second mixture mixing after, vibration, obtain final product the Kerosene Microemulsified
Liquid.
Preferably, the preparation method of described Kerosene Microemulsified liquid, the step one are specifically included:
Step a, it is passed through carbon dioxide in the kerosene of above-mentioned parts by weight, makes pressure reach 4~5MPa, keep 1~2h;
Step b, the kerosene that step a is obtained is divided into into three equal parts, by the cetyl trimethyl bromination of above-mentioned parts by weight
Ammonium is divided into two equal portions, to first part of kerosene using the 1~2min of ultrasonic irradiation of 20kHz, adds second part of kerosene and first part
Cetyl trimethylammonium bromide, using the 2~3min of ultrasonic irradiation of 30kHz, adds the 3rd part of kerosene and second part 16
Alkyl trimethyl ammonium bromide, using the 3~4min of ultrasonic irradiation of 40kHz;
Step c, the kerosene mixture that step b is obtained vacuumized remove unnecessary carbon dioxide, then ultrasonic atomization,
Send into the magnetic field that magnetic field intensity is 0.3T and process 3~5min, stand 1~2h, obtain final product the first mixture.
Preferably, the preparation method of described Kerosene Microemulsified liquid, the step 2 are specifically included:By above-mentioned parts by weight
Water magnetized water is obtained by magnetizer with 1m/s flow velocitys, add the glycine and phenylalanine mixture of above-mentioned parts by weight,
After stirring, multiple sponge blocks are placed thereto so as to fully immersion and absorption, insert the sealing dress for being provided with carborundum bullet
Put, the sealing device is connected with vibrating motor, with the frequency 3~5min of vibration processing of 10Hz, then fully extruding is described
Multiple sponge blocks, obtain final product the second mixture.
Preferably, the preparation method of described Kerosene Microemulsified liquid, the step 3 are specifically included:By the described first mixing
1~2min being vibrated after thing and second mixture mixing, then carrying out centrifugal treating, rotating speed is 600~800r/min, is kept
3~5min, obtains final product the Kerosene Microemulsified liquid.
The present invention at least includes following beneficial effect:
Firstth, the present invention selects a-amino acid to substitute traditional alcohols cosurfactant, and a-amino acid contains side chain
Group, can soften oil-water interfacial film, as amino and carboxyl are with reference on same carbon atom, prepare Kerosene Microemulsified liquid process
In, improve surface-active and the hydrophile-lipophile balance of surfactant, be conducive to the generation of Kerosene Microemulsified liquid, be initiative sending out
It is bright;
The side-chain radical of the secondth, glycine is hydrogen atom, and the side-chain radical of phenylalanine is aromatic group, glycine
Hydrophilicity, the hydrophobic performance of phenylalanine so that form competition in water/oil interface with surfactant, with surfactant
Intermolecular mutual repulsion, the instantaneous negative surface tension formed on interface, is conducive to the formation of microemulsion;
3rd, select cetyl trimethylammonium bromide as cationic surfactant, hydrophilic group is powered, have electrostatic to scold
Power, when micella is formed, selects glycine and phenylalanine as cosurfactant, makes distance between hydrophilic group become big, quiet
Electric repulsion diminishes, and makes oil mixing with water adsorbed film produce ultralow interfacial tension, makes oil mixing with water adsorbed film have certain pliability,
Interface is readily bent, and is conducive to the formation of microemulsion;
4th, obtained in the present invention, Kerosene Microemulsified liquid outward appearance clear, good stability, water content are high, have good burning performance,
Particle diameter is little, room temperature, high temperature, low temperature are placed without layering, does not contain the material that metal ion, element sulphur etc. are paid no attention to environment, helps
In burning completely, efficiency of combustion is improved;
5th, preparation method of the invention is passed through high-pressure carbon dioxide first in kerosene, can reduce kerosene viscosity, increasing
Coal oil elasticity simultaneously reduces the effect such as oil water interfacial tension, and kerosene is divided into three parts, successively with the Ultrasonic Radiation of frequency increments,
Local is produced by cavitation destruction tissue to crush so that kerosene and surfactant are well mixed, and vacuumize removal dioxy
Changing carbon prevents the dissolving of carbon dioxide, the kerosene after atomization is sent into magnetic field and is processed, and makes the physical arrangement in kerosene change,
The macromolecular of association chain fragments into single small molecule, suppresses Crystallization, removes irony impurity, fully reduces oil-water interfaces
Power;Glycine and phenylalanine are dissolved in magnetized water, and sponge block fully adsorbs swelling, then extrude under the bullet of vibration at high speed
Sponge block so that high-speed impact between molecule, forms uniform second mixture;High speed centrifugation promotes mixed effect, without layering
Phenomenon has good stability.
Part is embodied by the further advantage of the present invention, target and feature by description below, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, to make those skilled in the art with reference to specification
Word can be implemented according to this.
Embodiment 1:
A kind of Kerosene Microemulsified liquid, by 3.5mL kerosene, 1g cetyl trimethylammonium bromides, 0.006g glycine and phenylpropyl alcohol
The mixture of propylhomoserin, 1.98g water are made.
A kind of preparation method of Kerosene Microemulsified liquid, comprises the following steps:
Step one, in 3.5mL kerosene add 1g cetyl trimethylammonium bromides, stir, obtain the first mixture;
Step 2,0.006g glycine and phenylalanine and 1.98g water are well mixed, obtain the second mixture;
Step 3, by the first mixture and the second mixture mixing after, gently vibrate, obtain final product the Kerosene Microemulsified liquid.
The Kerosene Microemulsified liquid outward appearance clear that embodiment 1 is obtained, particle diameter is 49nm, and electrical conductivity is up to 3 × 103μ s/cm, contain
The water yield 47%, room temperature are placed and still keep within 1 year original proterties, have no that profit is layered, be heated to 60 DEG C and still keep original proterties, have no
Profit is layered, and melts and keeps original proterties, has no that profit is layered, measure fuel value, water mixing using Oxygen bomb after frost
20% Kerosene Microemulsified liquid, compared to pure kerosene, many 188J/g of fuel value.
Embodiment 2:
A kind of Kerosene Microemulsified liquid, by 6.25mL kerosene, 3g cetyl trimethylammonium bromides, 0.01g glycine and phenylpropyl alcohol
The mixture of propylhomoserin, 2g water are made.
A kind of preparation method of Kerosene Microemulsified liquid, comprises the following steps:
Step one, in 6.25mL kerosene add 3g cetyl trimethylammonium bromides, stir, obtain the first mixing
Thing;
Step 2,0.01g glycine and phenylalanine and 2g water are well mixed, obtain the second mixture;
Step 3, by the first mixture and the second mixture mixing after, gently vibrate, obtain final product the Kerosene Microemulsified liquid.
The Kerosene Microemulsified liquid outward appearance clear that embodiment 2 is obtained, particle diameter is 46nm, and electrical conductivity is up to 3 × 103μ s/cm, contain
The water yield 46%, room temperature are placed and still keep within 1 year original proterties, have no that profit is layered, be heated to 60 DEG C and still keep original proterties, have no
Profit is layered, and melts and keeps original proterties, has no that profit is layered, measure fuel value, water mixing using Oxygen bomb after frost
20% Kerosene Microemulsified liquid, compared to pure kerosene, many 195J/g of fuel value.
Embodiment 3:
A kind of Kerosene Microemulsified liquid, by 5mL kerosene, 2g cetyl trimethylammonium bromides, 0.008g glycine and phenylpropyl alcohol ammonia
The mixture of acid, 1.992g water are made.
A kind of preparation method of Kerosene Microemulsified liquid, comprises the following steps:
Step one, in 5mL kerosene add 2g cetyl trimethylammonium bromides, stir, obtain the first mixture;
Step 2,0.008g glycine and phenylalanine and 1.992g water are well mixed, obtain the second mixture;
Step 3, by the first mixture and the second mixture mixing after, gently vibrate, obtain final product the Kerosene Microemulsified liquid.
The Kerosene Microemulsified liquid outward appearance clear that embodiment 3 is obtained, particle diameter is 38nm, and electrical conductivity is up to 3 × 103μ s/cm, contain
The water yield 52%, room temperature are placed and still keep within 1 year original proterties, have no that profit is layered, be heated to 60 DEG C and still keep original proterties, have no
Profit is layered, and melts and keeps original proterties, has no that profit is layered, measure fuel value, water mixing using Oxygen bomb after frost
20% Kerosene Microemulsified liquid, compared to pure kerosene, many 201J/g of fuel value.
Embodiment 4:
A kind of Kerosene Microemulsified liquid, fills a prescription with embodiment 1.
A kind of preparation method of Kerosene Microemulsified liquid, comprises the following steps:
Step one,
Step a, it is passed through carbon dioxide in the kerosene of above-mentioned parts by weight, makes pressure reach 4MPa, keep 1h;
Step b, the kerosene that step a is obtained is divided into into three equal parts, by the cetyl trimethyl bromination of above-mentioned parts by weight
Ammonium is divided into two equal portions, to first part of kerosene using the ultrasonic irradiation 1min of 20kHz, adds second part of kerosene and first part 16
Alkyl trimethyl ammonium bromide, using the ultrasonic irradiation 2min of 30kHz, adds the 3rd part of kerosene and second part of cetyl front three
Base ammonium bromide, using the ultrasonic irradiation 3min of 40kHz;
Step c, the kerosene mixture that step b is obtained vacuumized remove unnecessary carbon dioxide, then ultrasonic atomization,
Send into the magnetic field that magnetic field intensity is 0.3T and process 3min, stand 1h, obtain final product the first mixture.
Step 2, the water of above-mentioned parts by weight is obtained into magnetized water with 1m/s flow velocitys by magnetizer, adds above-mentioned weight
The glycine and phenylalanine mixture of number, after stirring, places multiple sponge blocks thereto so as to fully immersion and suction
It is attached, the sealing device for being provided with carborundum bullet is inserted, the sealing device is connected with vibrating motor, vibrated with the frequency of 10Hz
3min is processed, the plurality of sponge block is then fully extruded, is obtained final product the second mixture.
Step 3, will first mixture and second mixture mixing after vibrate 1min, then carry out at centrifugation
Reason, rotating speed is 600r/min, keeps 3min, obtains final product the Kerosene Microemulsified liquid.
The Kerosene Microemulsified liquid outward appearance clear that embodiment 4 is obtained, particle diameter is 37nm, and electrical conductivity is up to 3 × 103μ s/cm, contain
The water yield 56%, room temperature are placed and still keep within 1 year original proterties, have no that profit is layered, be heated to 60 DEG C and still keep original proterties, have no
Profit is layered, and melts and keeps original proterties, has no that profit is layered, measure fuel value, water mixing using Oxygen bomb after frost
20% Kerosene Microemulsified liquid, compared to pure kerosene, many 215J/g of fuel value.
The preparation method that embodiment 4 is adopted, compared to embodiment 1, can promote being sufficiently mixed for each component, mix profit
Close adsorbed film and produce ultralow interfacial tension, obtained Kerosene Microemulsified liquid form is more preferable, stability more preferable, water content is higher, burning
Performance is more preferable.
Embodiment 5:
A kind of Kerosene Microemulsified liquid, fills a prescription with embodiment 2.
A kind of preparation method of Kerosene Microemulsified liquid, comprises the following steps:
Step one,
Step a, it is passed through carbon dioxide in the kerosene of above-mentioned parts by weight, makes pressure reach 5MPa, keep 2h;
Step b, the kerosene that step a is obtained is divided into into three equal parts, by the cetyl trimethyl bromination of above-mentioned parts by weight
Ammonium is divided into two equal portions, to first part of kerosene using the ultrasonic irradiation 2min of 20kHz, adds second part of kerosene and first part 16
Alkyl trimethyl ammonium bromide, using the ultrasonic irradiation 3min of 30kHz, adds the 3rd part of kerosene and second part of cetyl front three
Base ammonium bromide, using the ultrasonic irradiation 4min of 40kHz;
Step c, the kerosene mixture that step b is obtained vacuumized remove unnecessary carbon dioxide, then ultrasonic atomization,
Send into the magnetic field that magnetic field intensity is 0.3T and process 5min, stand 2h, obtain final product the first mixture.
Step 2, the water of above-mentioned parts by weight is obtained into magnetized water with 1m/s flow velocitys by magnetizer, adds above-mentioned weight
The glycine and phenylalanine mixture of number, after stirring, places multiple sponge blocks thereto so as to fully immersion and suction
It is attached, the sealing device for being provided with carborundum bullet is inserted, the sealing device is connected with vibrating motor, vibrated with the frequency of 10Hz
5min is processed, the plurality of sponge block is then fully extruded, is obtained final product the second mixture.
Step 3, will first mixture and second mixture mixing after vibrate 2min, then carry out at centrifugation
Reason, rotating speed is 800r/min, keeps 5min, obtains final product the Kerosene Microemulsified liquid.
The Kerosene Microemulsified liquid outward appearance clear that embodiment 5 is obtained, particle diameter is 33nm, and electrical conductivity is up to 3 × 103μ s/cm, contain
The water yield 52%, room temperature are placed and still keep within 1 year original proterties, have no that profit is layered, be heated to 60 DEG C and still keep original proterties, have no
Profit is layered, and melts and keeps original proterties, has no that profit is layered, measure fuel value, water mixing using Oxygen bomb after frost
20% Kerosene Microemulsified liquid, compared to pure kerosene, many 211J/g of fuel value.
The preparation method that embodiment 5 is adopted, compared to embodiment 2, can promote being sufficiently mixed for each component, mix profit
Close adsorbed film and produce ultralow interfacial tension, obtained Kerosene Microemulsified liquid form is more preferable, stability more preferable, water content is higher, burning
Performance is more preferable.
Embodiment 6:
A kind of Kerosene Microemulsified liquid, fills a prescription with embodiment 3.
A kind of preparation method of Kerosene Microemulsified liquid, comprises the following steps:
Step one,
Step a, it is passed through carbon dioxide in the kerosene of above-mentioned parts by weight, makes pressure reach 4.5MPa, keep 1.5h;
Step b, the kerosene that step a is obtained is divided into into three equal parts, by the cetyl trimethyl bromination of above-mentioned parts by weight
Ammonium is divided into two equal portions, to first part of kerosene using the ultrasonic irradiation 1.5min of 20kHz, adds second part of kerosene and first part ten
Six alkyl trimethyl ammonium bromides, using the ultrasonic irradiation 2.5min of 30kHz, add the 3rd part of kerosene and second part of cetyl
Trimethylammonium bromide, using the ultrasonic irradiation 3.5min of 40kHz;
Step c, the kerosene mixture that step b is obtained vacuumized remove unnecessary carbon dioxide, then ultrasonic atomization,
Send into the magnetic field that magnetic field intensity is 0.3T and process 4min, stand 1.5h, obtain final product the first mixture.
Step 2, the water of above-mentioned parts by weight is obtained into magnetized water with 1m/s flow velocitys by magnetizer, adds above-mentioned weight
The glycine and phenylalanine mixture of number, after stirring, places multiple sponge blocks thereto so as to fully immersion and suction
It is attached, the sealing device for being provided with carborundum bullet is inserted, the sealing device is connected with vibrating motor, vibrated with the frequency of 10Hz
4min is processed, the plurality of sponge block is then fully extruded, is obtained final product the second mixture.
Step 3, will first mixture and second mixture mixing after vibrate 1.5min, be then centrifuged
Process, rotating speed is 700r/min, keep 4min, obtain final product the Kerosene Microemulsified liquid.
The Kerosene Microemulsified liquid outward appearance clear that embodiment 6 is obtained, particle diameter is 28nm, and electrical conductivity is up to 3 × 103μ s/cm, contain
The water yield 66%, room temperature are placed and still keep within 1 year original proterties, have no that profit is layered, be heated to 60 DEG C and still keep original proterties, have no
Profit is layered, and melts and keeps original proterties, has no that profit is layered, measure fuel value, water mixing using Oxygen bomb after frost
20% Kerosene Microemulsified liquid, compared to pure kerosene, many 225J/g of fuel value.
The preparation method that embodiment 6 is adopted, compared to embodiment 3, can promote being sufficiently mixed for each component, mix profit
Close adsorbed film and produce ultralow interfacial tension, obtained Kerosene Microemulsified liquid form is more preferable, stability more preferable, water content is higher, burning
Performance is more preferable.
Comparative example 1:
A kind of Kerosene Microemulsified liquid and preparation method thereof, with embodiment 3, by 0.008g glycine and the mixture of phenylalanine
Replace with 0.008g n-butanols.
The Kerosene Microemulsified liquid translucent appearance that comparative example 1 is obtained, particle diameter is 78nm, and electrical conductivity is up to 1 × 103μ s/cm, it is aqueous
Amount 34%, room temperature place and keep within 1 month original proterties, have no that profit is layered that profit layering after 1 year is heated to 60 DEG C of profits point
Layer, melts profit layering, measures fuel value using Oxygen bomb after frost, the Kerosene Microemulsified liquid of water mixing 20%, compared to pure
Kerosene, many 105J/g of fuel value.
Embodiment 3 and comparative example 1 are compared and are obtained, and a-amino acid can improve surfactant as cosurfactant
Surface-active and hydrophile-lipophile balance, and soften oil-water interfacial film, outward appearance clear, good stability, water content be obtained
It is high, have good burning performance, particle diameter is little, room temperature, high temperature, low temperature place the Kerosene Microemulsified liquid without layering, does not contain metal ion, sulphur unit
The material that element etc. is paid no attention to environment, contributes to burning completely, improves efficiency of combustion.
Comparative example 2:
A kind of Kerosene Microemulsified liquid and preparation method thereof, with embodiment 6, by 0.008g glycine and the mixture of phenylalanine
Replace with 0.008g n-butanols.
The Kerosene Microemulsified liquid translucent appearance that comparative example 2 is obtained, particle diameter is 65nm, and electrical conductivity is up to 2 × 103μ s/cm, it is aqueous
Amount 42%, room temperature place and keep within 1 month original proterties, have no that profit is layered that profit layering after 1 year is heated to 60 DEG C of profits point
Layer, melts after frost and has no that profit is layered, measure fuel value using Oxygen bomb, and the Kerosene Microemulsified liquid of water mixing 20% is compared
In pure kerosene, many 145J/g of fuel value.
Embodiment 6 and comparative example 2 are compared and are obtained, and a-amino acid can improve surfactant as cosurfactant
Surface-active and hydrophile-lipophile balance, and soften oil-water interfacial film, outward appearance clear, good stability, water content be obtained
It is high, have good burning performance, particle diameter is little, room temperature, high temperature, low temperature place the Kerosene Microemulsified liquid without layering, does not contain metal ion, sulphur unit
The material that element etc. is paid no attention to environment, contributes to burning completely, improves efficiency of combustion.
Although embodiment of the present invention is disclosed as above, which is not restricted to listed by specification and embodiment
With, it can be applied to various suitable the field of the invention completely, for those skilled in the art, can be easily
Other modification is realized, therefore under the universal limited without departing substantially from claim and equivalency range, the present invention is not limited
In specific details and shown here as the embodiment with description.
Claims (1)
1. a kind of preparation method of Kerosene Microemulsified liquid, it is characterised in that comprise the following steps:
Step one, add 100~300 weight portion cetyl trimethylammonium bromides in 300~500 weight portion kerosene, obtain the
One mixture;
Step 2, the mixture for adding 0.6~1 weight portion glycine and phenylalanine in 198~200 weight portion water, obtain the
Two mixtures;
Step 3, by first mixture and second mixture mixing after, vibration, obtain final product the Kerosene Microemulsified liquid.
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FR2480775A1 (en) * | 1980-04-16 | 1981-10-23 | Elf France | PROCESS FOR IMPROVING THE PHYSICO-CHEMICAL CHARACTERISTICS OF GASOIL COMBUSTION |
FR2505866A1 (en) * | 1981-05-15 | 1982-11-19 | Elf Aquitaine | IMPROVED FUEL BASED ON HYDROCARBONS CONTAINING ALCOHOL |
US6302929B1 (en) * | 1994-04-04 | 2001-10-16 | Rudolf W. Gunnerman | Aqueous fuel for internal combustion engine and method of preparing |
US20060201056A1 (en) * | 2000-04-14 | 2006-09-14 | Oryxe Energy International, Inc. | Biodiesel fuel additive |
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