WO2011154001A1 - Emulsified oxygenate diesel fuel composition and method of preparing an emulsified oxygenate diesel fuel composition - Google Patents
Emulsified oxygenate diesel fuel composition and method of preparing an emulsified oxygenate diesel fuel composition Download PDFInfo
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- WO2011154001A1 WO2011154001A1 PCT/DK2011/000055 DK2011000055W WO2011154001A1 WO 2011154001 A1 WO2011154001 A1 WO 2011154001A1 DK 2011000055 W DK2011000055 W DK 2011000055W WO 2011154001 A1 WO2011154001 A1 WO 2011154001A1
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- diesel fuel
- fuel composition
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- emulsifier
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
- C10L1/328—Oil emulsions containing water or any other hydrophilic phase
-
- 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
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
- C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
-
- 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
- C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
-
- 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
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
- C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
-
- 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
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
- C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
Definitions
- the present invention relates to an emulsified oxygenate diesel fuel composition consisting of water, an alcohol and an ether together with a water/oil emulsifier and an oil/water emulsifier.
- the invention further relates to a method of preparing the emulsified fuel composition on board a vehicle for use as fuel in a compression ignition engine.
- Diesel fuel To reduce environmental pollution arising from combustion of Diesel fuel, several attempts have been made in the past to replace Diesel fuel with alternative fuels having a reduced impact on the environment .
- Ethers in particular ethers prepared by dehydration of lower alcohols, such as dimethyl and diethyl ether, have shown to be a superior Diesel fuel.
- lower ethers as Diesel fuel has been described in a number of publications, e.g. US Patent Nos. 4,892,561, 5,906,664 and 7,449,034.
- dimethyl ether is in the gaseous form at ambient conditions.
- the fuel must be stored and handled under pressure .
- US patent No. 7,449,034 discloses oxygenated Diesel fuel compositions, which contain a combination of alcohol, ether and water.
- the fuel compositions are prepared by means of a catalytic dehydration unit on board a vehicle.
- Modern Diesel engines are provided with a common rail fuel system.
- the system consists of a high pressure pump and a fuel accumulation chamber for storing fuel at high
- the accumulation chamber supplies multiple fuel injectors with high pressure fuel. Surplus fuel is withdrawn from the chamber, depressurised and recycled to a fuel buffer tank. During conversion of alcohol into ether, water is
- phase separation may occur in the buffer tank of the common rail system resulting in an in-homogeneous fuel to the engine.
- phase separation occurs in the buffer tank, slugging in the feed rail system may lead to imbalance in the engine performance .
- this invention provides an emulsified oxygenate diesel fuel composition comprising water and an ether and optionally an alcohol together with a water/oil emulsifier having an HLB value of between 4 and 6 and an oil/water emulsifier having an HLB value of between 8 and 13.
- HLB Hydrophilic-Lipophilic Balance
- said measure being determined by calculating values for the different regions of the molecule as
- HLB 20 * Mh / where Mh is the molecular mass of the hydrophilic portion of the molecule, and M is the molecular mass of the whole molecule giving a result on an arbitrary scale of 0 to 20.
- An HLB value of 0 corresponds to a completely hydrophobic molecule, and a value of 20 corresponds to a molecule made completely of hydrophilic components.
- the alcohol of the emulsified diesel fuel according to the invention comprises preferably methanol, ethanol or
- the ether comprises dimethyl ether, diethyl ether, methyl-ethyl ether or mixtures thereof.
- the content of water is typically between 10 and 50 wt%, the content of the alcohol between 0 and 25 wt% and the content of the ether between 40 and 90 wt%, which provide an excellent engine performance.
- the amount of emulsifier is preferably between 0.05 and 5 vol% based on the total oxygenated diesel fuel product (ether/water/alcohol) , and the ratio of the water/oil emulsifier to the oil/water emulsifier is between 1:2 and 2:1.
- Preferred water/oil emulsifiers for use in the invention comprise sorbitan oleates, in particular sorbitan
- sorbitan (Z)-mono-9- octadecenoate being commercially available under the trade mark Span ® 80.
- Preferred oil/water emulsifiers comprise alkylphenol ethoxylates, in particular octylphenol ethoxylate being commercially available under the trade mark TRITONTM X-45.
- An amount of surfactant/emulsifier capable of stabilizing a water in an oil emulsion system (HLB number ⁇ 10) is injected into the reactor product stream, preferably at the valve system of the reactor, where the pressure is released or before a restriction after said valve system, or just after the feed pump for the injection system.
- HLB number ⁇ 10 An amount of surfactant/emulsifier capable of stabilizing a water in an oil emulsion system (HLB number ⁇ 10) is injected into the reactor product stream, preferably at the valve system of the reactor, where the pressure is released or before a restriction after said valve system, or just after the feed
- the amount of surfactant can be between 0.05 and 5% based on the total fuel composition e.g. DEE/water/ethanol.
- the role of the surfactant is to decrease the rate of static separation and to allow for a rapid and easy re-dispersion after the phase separation, i.e. in case of parking the vehicle. Further the surfactant may add to increase the lubricity which is lacking in diethyl ether containing fuel compositions compared to traditional diesel fuel .
- the invention provides a method of preparing an emulsified oxygenate diesel fuel.
- the method comprises the steps of contacting an alcohol primary fuel with one or more dehydration catalysts; dehydrating the alcohol to its corresponding ether and water; and adding an amount of a water/oil emulsifier having an HLB value of between 4 and 6 and an oil/water emulsifier having an HLB value of between 8 and 13 to an alcohol primary fuel.
- the method comprises the steps of adding an amount of a water/oil emulsifier having an HLB value of between 4 and 6 and a oil/water emulsifier having an HLB value of between 8 and 13 to an alcohol primary fuel; contacting the primary fuel containing the water/oil and oil/water emulsifier with one or more alcohol dehydration catalysts and dehydrating the alcohol to its corresponding ether and water.
- Sorbitan monooleat emulsifier Span ® 80 was added to a 1:1 weight mixture of ethanol and water and dispersed by shaking. The SPAN concentration was varied from 0.2 to 2.5 wt% of the final mixture. Further 2 weight parts of diethyl ether (DEE) were added, and the mixture was shaken by hand for 2 minutes. After this phase volumes were estimated as a function of time. Rapid creaming was observed (decreasing haze of upper part of test tube) , while a slow formation of the bottom phase appeared.
- DEE diethyl ether
- Sorbitan monooleat emulsifier Span ® 80 and the dispersant TRITONTM X-45 were added in equal amounts to a 1:1 weight mixture of ethanol and water and dispersed by shaking.
- the Span ® 80 concentration was varied from 0.2 to 2.5 wt% of the final mixture. Further 2 weight parts of DEE were added, and the mixture was shaken by hand for 2 minutes. No settling of a lower phase was observed within one hour, while a weak creaming of a clear top phase was observed.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
Emulsified oxygenate diesel fuel composition comprising water and an ether together with a water/oil emulsifier and an oil/water emulsifier, and a method of preparing the same.
Description
Title : Emulsified Oxygenate Diesel Fuel Composition and Method of preparing an Emulsified Oxygenate Diesel Fuel Composition The present invention relates to an emulsified oxygenate diesel fuel composition consisting of water, an alcohol and an ether together with a water/oil emulsifier and an oil/water emulsifier. The invention further relates to a method of preparing the emulsified fuel composition on board a vehicle for use as fuel in a compression ignition engine.
The most typical example of a compression ignition engine is the Diesel engine operating with high cetane numbered
Diesel fuel. To reduce environmental pollution arising from combustion of Diesel fuel, several attempts have been made in the past to replace Diesel fuel with alternative fuels having a reduced impact on the environment .
Ethers, in particular ethers prepared by dehydration of lower alcohols, such as dimethyl and diethyl ether, have shown to be a superior Diesel fuel. The use of lower ethers as Diesel fuel has been described in a number of publications, e.g. US Patent Nos. 4,892,561, 5,906,664 and 7,449,034.
Despite its clean combustion characteristics and high efficiency in a Diesel engine, the main disadvantage of an ether-based fuel is found in the difficult storage and handling thereof on board vehicles. As an example, dimethyl
ether is in the gaseous form at ambient conditions. To transform the dimethyl ether fuel into its more convenient liquid form, the fuel must be stored and handled under pressure .
To avoid storage of ethers on board a vehicle, US patent No. 7,449,034 discloses oxygenated Diesel fuel compositions, which contain a combination of alcohol, ether and water. The fuel compositions are prepared by means of a catalytic dehydration unit on board a vehicle.
Modern Diesel engines are provided with a common rail fuel system. The system consists of a high pressure pump and a fuel accumulation chamber for storing fuel at high
pressures of above 2,000 bars. The accumulation chamber supplies multiple fuel injectors with high pressure fuel. Surplus fuel is withdrawn from the chamber, depressurised and recycled to a fuel buffer tank. During conversion of alcohol into ether, water is
cogenerated, and at a certain level of conversion two liquid phases in equilibrium may be formed. Thus, when operating an engine system on oxygenated diesel fuel prepared on board by dehydration of a primary alcohol fuel phase, phase separation may occur in the buffer tank of the common rail system resulting in an in-homogeneous fuel to the engine.
When phase separation occurs in the buffer tank, slugging in the feed rail system may lead to imbalance in the engine performance .
It has now been found that phase separation of an oxygenate diesel fuel is avoided by^adding a water/oil emulsifier together with an oil/water emulsifier to the fuel. Pursuant to this finding, this invention provides an emulsified oxygenate diesel fuel composition comprising water and an ether and optionally an alcohol together with a water/oil emulsifier having an HLB value of between 4 and 6 and an oil/water emulsifier having an HLB value of between 8 and 13.
The term "HLB" is commonly known in the art as a shortage of "Hydrophilic-Lipophilic Balance". The hydrophilic-lipophilic balance of an emulsifier is a measure of the degree to which it is hydrophilic or
lipophilic, said measure being determined by calculating values for the different regions of the molecule as
described by Griffin (Griffin WC: "Classification of
Surface-Active Agents by 'HLB,'" Journal of the Society of Cosmetic Chemists 1 (1949) : 311; and Griffin WC:
"Calculation of HLB Values of Non-Ionic Surfactants,"
Journal of the Society of Cosmetic Chemists 5 (1954) : 259) . The HLB value of an emulsifier is calculated according to the following formula:
HLB = 20 * Mh / where Mh is the molecular mass of the hydrophilic portion of the molecule, and M is the molecular mass of the whole molecule giving a result on an arbitrary scale of 0 to 20.
An HLB value of 0 corresponds to a completely hydrophobic molecule, and a value of 20 corresponds to a molecule made completely of hydrophilic components. Other correlations exist for specific molecular types of emulsifiers, said correlations taking into account
variations in e.g. number of . repeating units.
The alcohol of the emulsified diesel fuel according to the invention comprises preferably methanol, ethanol or
mixtures thereof, and the ether comprises dimethyl ether, diethyl ether, methyl-ethyl ether or mixtures thereof.
In the emulsified fuel, the content of water is typically between 10 and 50 wt%, the content of the alcohol between 0 and 25 wt% and the content of the ether between 40 and 90 wt%, which provide an excellent engine performance.
The amount of emulsifier is preferably between 0.05 and 5 vol% based on the total oxygenated diesel fuel product (ether/water/alcohol) , and the ratio of the water/oil emulsifier to the oil/water emulsifier is between 1:2 and 2:1. Preferred water/oil emulsifiers for use in the invention comprise sorbitan oleates, in particular sorbitan
monooctadecanoate, such as sorbitan (Z)-mono-9- octadecenoate being commercially available under the trade mark Span® 80.
Preferred oil/water emulsifiers comprise alkylphenol ethoxylates, in particular octylphenol ethoxylate being commercially available under the trade mark TRITON™ X-45. An amount of surfactant/emulsifier capable of stabilizing a water in an oil emulsion system (HLB number < 10) is injected into the reactor product stream, preferably at the valve system of the reactor, where the pressure is released or before a restriction after said valve system, or just after the feed pump for the injection system. As a' result, sufficient energy is provided for the emulsification of the two liquid phases without any other means. To enable a sufficient mixing, the surfactant must be delivered in a water/ethanol solution or dispersion.
The amount of surfactant can be between 0.05 and 5% based on the total fuel composition e.g. DEE/water/ethanol. The sedimentation and equilibrium phase separation of
DEE/water/ethanol mixtures into two liquid phases appears within minutes. The role of the surfactant is to decrease the rate of static separation and to allow for a rapid and easy re-dispersion after the phase separation, i.e. in case of parking the vehicle. Further the surfactant may add to increase the lubricity which is lacking in diethyl ether containing fuel compositions compared to traditional diesel fuel .
In addition, the invention provides a method of preparing an emulsified oxygenate diesel fuel.
In one embodiment of the invention, the method comprises the steps of
contacting an alcohol primary fuel with one or more dehydration catalysts; dehydrating the alcohol to its corresponding ether and water; and adding an amount of a water/oil emulsifier having an HLB value of between 4 and 6 and an oil/water emulsifier having an HLB value of between 8 and 13 to an alcohol primary fuel.
In a further embodiment of the invention, the method comprises the steps of adding an amount of a water/oil emulsifier having an HLB value of between 4 and 6 and a oil/water emulsifier having an HLB value of between 8 and 13 to an alcohol primary fuel; contacting the primary fuel containing the water/oil and oil/water emulsifier with one or more alcohol dehydration catalysts and dehydrating the alcohol to its corresponding ether and water.
EXAMPLES
Example 1 (comparative)
Sorbitan monooleat emulsifier Span® 80 was added to a 1:1 weight mixture of ethanol and water and dispersed by
shaking. The SPAN concentration was varied from 0.2 to 2.5 wt% of the final mixture. Further 2 weight parts of diethyl ether (DEE) were added, and the mixture was shaken by hand for 2 minutes. After this phase volumes were estimated as a function of time. Rapid creaming was observed (decreasing haze of upper part of test tube) , while a slow formation of the bottom phase appeared.
Example 2
Sorbitan monooleat emulsifier Span® 80 and the dispersant TRITON™ X-45 were added in equal amounts to a 1:1 weight mixture of ethanol and water and dispersed by shaking. The Span® 80 concentration was varied from 0.2 to 2.5 wt% of the final mixture. Further 2 weight parts of DEE were added, and the mixture was shaken by hand for 2 minutes. No settling of a lower phase was observed within one hour, while a weak creaming of a clear top phase was observed.
Claims
1. Emulsified oxygenate diesel fuel composition comprising water, an ether and optionally an alcohol together with a water/oil emulsifier having an HLB value of between 4 and 6 and an oil/water emulsifier having an HLB value of between 8 and 13.
2. The diesel fuel composition of claim 1, wherein the ether comprises dimethyl ether, diethyl ether, methyl- ethyl ether or mixtures thereof.
3. The diesel fuel composition of claim 1 or 2, wherein the water/oil emulsifier comprises a sorbitan oleate.
4. The diesel fuel composition in accordance with anyone of claims 1 to 3, wherein the oil/water emulsifier comprises an alkylphenol ethoxylate.
5. The diesel fuel composition of claim 3, wherein the sorbitan oleate is sorbitan monooctadecanoate .
6. The diesel fuel composition of claim 4, wherein the alkylphenol ethoxylate is octylphenol ethoxylate.
7. The diesel fuel composition in accordance with anyone of claims 1 to 6, wherein the content of water is between 10 and 50 wt%, the content of alcohol is between 0 and 25 wt%, and the content of ether is between 40 and 90 wt% .
8. The diesel fuel composition in accordance with anyone of claims 1 to 7, wherein the ratio of the water/oil emulsifier to the oil/water emulsifier is between 1:2 and 2:1.
9. The diesel fuel composition in accordance with anyone of claims 1 to 8, wherein the content of the
water/oil emulsifier is between 0.02 and 3 wt% of the diesel fuel composition and the oil/water emulsifier is between 0.02 and 3 wt% of the diesel fuel composition.
10. The diesel fuel composition in accordance with anyone of claims 1 to 9, wherein the alcohol is selected from methanol, ethanol and mixtures thereof, and the ether is selected from dimethyl ether, diethyl ether and mixtures thereof.
11. Method of preparing an emulsified oxygenate, diesel fuel composition, comprising the steps of contacting an alcohol primary fuel with one or more
dehydration catalysts; dehydrating the alcohol to an oxygenate diesel fuel
comprising an ether and water; and adding an amount of a water/oil emulsifier having an HLB value of between 4 and 6 and an oil/water emulsifier having an HLB value of between 8 and 13 to the oxygenate diesel fuel.
12. Method of preparing an emulsified oxygenate diesel fuel composition, comprising the steps of adding an amount of a water/oil emulsifier having an HLB value of between 4 and 6 and an oil/water emulsifier having an HLB value of between 8 and 13 to an alcohol primary fuel; contacting the primary fuel containing the water/oil and oil/water emulsifier with one or more alcohol dehydration catalysts and dehydrating the alcohol to its corresponding ether and water.
13. The method of claim 11 or 12, wherein the alcohol is selected from methanol, ethanol and mixtures thereof.
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DKPA201000494 | 2010-06-09 | ||
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103805299A (en) * | 2014-03-13 | 2014-05-21 | 黑龙江省能源环境研究院 | Methyl alcohol emulsified diesel oil and preparation method thereof |
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US6068670A (en) * | 1996-03-15 | 2000-05-30 | Elf Antar France (Societe Anonyme) | Emulsified fuel and one method for preparing same |
WO2002064708A2 (en) * | 2000-12-06 | 2002-08-22 | The Lubrizol Corporation | A continuous process for making an aqueous hydrocarbon fuel emulsion |
WO2003002693A2 (en) * | 2001-06-26 | 2003-01-09 | The Lubrizol Corporation | Amino alkylphenol emulsifiers for an aqueous hydrocarbon fuel |
US20040111955A1 (en) * | 2002-12-13 | 2004-06-17 | Mullay John J. | Emulsified water blended fuels produced by using a low energy process and novel surfuctant |
US20060048443A1 (en) * | 1998-09-14 | 2006-03-09 | Filippini Brian B | Emulsified water-blended fuel compositions |
US20070119529A1 (en) * | 2003-04-30 | 2007-05-31 | David Hobson | Ethoxylated surfactants for water in oil emulsions |
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2011
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US6068670A (en) * | 1996-03-15 | 2000-05-30 | Elf Antar France (Societe Anonyme) | Emulsified fuel and one method for preparing same |
US20060048443A1 (en) * | 1998-09-14 | 2006-03-09 | Filippini Brian B | Emulsified water-blended fuel compositions |
WO2002064708A2 (en) * | 2000-12-06 | 2002-08-22 | The Lubrizol Corporation | A continuous process for making an aqueous hydrocarbon fuel emulsion |
WO2003002693A2 (en) * | 2001-06-26 | 2003-01-09 | The Lubrizol Corporation | Amino alkylphenol emulsifiers for an aqueous hydrocarbon fuel |
US20040111955A1 (en) * | 2002-12-13 | 2004-06-17 | Mullay John J. | Emulsified water blended fuels produced by using a low energy process and novel surfuctant |
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CN103805299A (en) * | 2014-03-13 | 2014-05-21 | 黑龙江省能源环境研究院 | Methyl alcohol emulsified diesel oil and preparation method thereof |
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