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WO2015110982A1 - Mélange émulsifiant et son utilisation - Google Patents

Mélange émulsifiant et son utilisation Download PDF

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Publication number
WO2015110982A1
WO2015110982A1 PCT/IB2015/050490 IB2015050490W WO2015110982A1 WO 2015110982 A1 WO2015110982 A1 WO 2015110982A1 IB 2015050490 W IB2015050490 W IB 2015050490W WO 2015110982 A1 WO2015110982 A1 WO 2015110982A1
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WO
WIPO (PCT)
Prior art keywords
fuel
glycol
mixture
emulsion
component
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.)
Ceased
Application number
PCT/IB2015/050490
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English (en)
Inventor
Giangluigi CAREVAGGINI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NEST Srl
Original Assignee
NEST Srl
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Filing date
Publication date
Application filed by NEST Srl filed Critical NEST Srl
Publication of WO2015110982A1 publication Critical patent/WO2015110982A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C10L1/328—Oil emulsions containing water or any other hydrophilic phase
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C10L2200/0446—Diesel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C10L2200/0484—Vegetable or animal oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2250/00—Structural features of fuel components or fuel compositions, either in solid, liquid or gaseous state
    • C10L2250/08—Emulsion details
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2250/00—Structural features of fuel components or fuel compositions, either in solid, liquid or gaseous state
    • C10L2250/08—Emulsion details
    • C10L2250/084—Water in oil (w/o) emulsion

Definitions

  • the present invention relates to the field of the emulsifiers, in particular to an emulsifying mixture and its use as an additive for fuel/water emulsified mixtures.
  • water promotes the process of fuel particles dispersion during the combustion phase.
  • the engine is more efficient and disperses a lower amount of particulate and of partial oxidation products (carbon black, carbon monoxide, etc.).
  • surfactants which promote the formation of stable emulsions of hydrophilic and hydrophobic compounds.
  • Zhang uses a complex mixture of sorbitan mono-oleate, polyoxyethylene alkylphenol, sodium alkylbenzene sulfonate and sodium carboxymethylcellulose, obtaining a maximum amount of emulsified water equal to 14 wt%, relative to the overall fuel.
  • Fumagalli has recently filed the patent application WO2013/098630, which describes, as a solution to the problems associated to the emulsifying of water and diesel fuel, the use of a multi-component mixture consisting of a mixture of five compounds, including 1 .
  • Esters of unsaturated fats 2. the condensation products between an unsaturated fatty acid and an alkanolamine, 3. the condensation product between an unsaturated fatty acid and an ethylene oxide, 4. esters of sorbitanalkoxylate, 5. an alcohol ethoxylate.
  • Esters of unsaturated fats 2. the condensation products between an unsaturated fatty acid and an alkanolamine, 3. the condensation product between an unsaturated fatty acid and an ethylene oxide, 4. esters of sorbitanalkoxylate, 5. an alcohol ethoxylate.
  • esters of sorbitanalkoxylate 5. an alcohol ethoxylate.
  • sorbitan since in that patent derivatives of sorbitan are used, they cannot be guaranteed the inhibitor
  • emulsifying products An alternative to the use of emulsifying products is the use of micronizers and microemulsifier, capable of producing fuel particles of micrometric dimensions that, without adding further components, emulsify "spontaneously".
  • micronizers and microemulsifier capable of producing fuel particles of micrometric dimensions that, without adding further components, emulsify "spontaneously".
  • no details are available regarding the stability of such compound, neither during the storage period neither during the use.
  • a partial separation of the emulsion during the pumping could lead the water in contact with gears and pipes, causing problems of different nature.
  • the combustion would be less effective, invalidating the effects of the emulsification process.
  • the presence of "free" water would lead to damages of the engine components (injectors, piping, sensors, etc.).
  • microemulsions using mechanical equipment requires specially designed (vaporizers, pumps, condensers, etc.), not allowing an immediate use by the end user, since the latter must first of the required instrumentation.
  • one consists in the addition of anti-corrosion components, as in Patent WO99/63026.
  • the final mixture contains also lubricants, anticorrosion products and antifreeze products.
  • the amount of pollutant emissions is only partially reduced, not reaching, however, the values obtained with other types of emulsions.
  • the State of the Art proposes numerous and heterogeneous solutions to such problems. However no solutions, with an easy and inexpensive manufacturing, still emerge, in order to allow the simultaneously solution to the problems listed above.
  • the aim of the present invention is to provide an additive (composed of one or more chemical compounds) capable of emulsifying mixtures consisting of water and hydrophobic substances (fuels), in order to obtain fuels to be used in internal combustion engines, for the production of mechanical, electrical or thermal energy.
  • the aim of the present invention is also:
  • the Applicant has developed, through a simple procedure, a two- component emulsifier mixture, obtainable from renewable raw materials.
  • the present invention solves the above-described problems using an emulsifying mixture consisting of the following two components:
  • weight ratio A:B ranges from 65:35 to 80:20.
  • the above emulsifier mixture is particularly useful to form water/fuel emulsions.
  • Subject of the present invention is therefore also a fuel emulsion, wherein the amount of emulsified water can also reach up to 35 wt%, said emulsion comprising the emulsifying mixture according to the invention.
  • These emulsions have proved to be stable for at least 3 months and have shown that they can be used in internal combustion devices, without substantial changes to the mechanical system; to obtain output powers from the engine, fuelled by these emulsions, comparable with those provided in using exclusively non-emulsified fuel and to achieve significant reductions of particulate amount and greenhouse gases emitted by the exhausts.
  • long-chain fatty acid means a carboxylic acid with aliphatic chain composed of a number of carbon atoms comprised between 14 and 20; said aliphatic chain may be saturated, polyunsaturated or monounsaturated.
  • This definition includes palmitic acid, margaric acid, stearic acid, arachidic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, linoleic, linolenic acid, stearidonic acid, arachidonic acid, timnodonic acid.
  • the component (A) is the mixture obtained at the end of a partial transesterification reaction of a vegetable oil with glycol or glycerine.
  • Said vegetable oil is preferably selected from the group consisting of sunflower oil, rapeseed oil, mixed seeds oil, corn oil.
  • Said glycol is preferably selected from the group consisting of diethylene glycol, triethylene glycol, tetraethylene glycol.
  • glycerine As alternative to the glycol, it is possible to use glycerine.
  • Said transesterification may be performed in presence of a molar ratio of vegetable oil/glycol ranging from 1 :1 to 1 :2.5.
  • Said transesterification is preferably carried out using the vegetable oil itself as solvent and heating the mixture oil/glycol at 100-200 °C (preferably 120-170 °C) in the presence of an alkaline catalyst (such as K2CO3) .
  • an alkaline catalyst such as K2CO3
  • component A is constituted by the mixture of transesterification reaction between corn oil and glycerol in the molar ratio 1 :2 (in order to obtain as the main product monoglycerides of the fatty acids contained in theseed oil).
  • the component (B) is the mixture obtained of a salification reaction of a long chain fatty acid with an amine compound (i.e., ammonia or an amine).
  • an amine compound i.e., ammonia or an amine
  • said salified long chain fatty acid is selected from the group consisting of oleic, linoleic, stearic, palmitic, linolenic.
  • Said ammonia is preferably (and advantageously) in the formulation of an aqueous solution, commonly available as 30 wt%.
  • Said amine may be primary, secondary or tertiary; preferably, said amine is selected from the group consisting of ethanolamine, diethanolamine, triethanolamine, ethylenediamine, tetraetilendiamine, diazobicyclooctane and methylamine.
  • component (B) is the ammonium salt of oleic acid.
  • the components (A) and (B) are mixed in weight ratios comprised between 65:35 and 75:25; more preferably 70:30.
  • the present invention relates to a process for prepraring the emulsifying mixture as above described, said process comprising:
  • component (B) - mixing of component (A) with component (B).
  • component (B) it is possible to dilute with a small amount of an aqueous solvent, or alcohol or mixtures thereof, if necessary to make the mixture stirrable. If 30% aqueous ammonia is used, further dilutions are not necessary. In some cases, it is possible to prepare component (B) directly in a mixture containing the component (A).
  • the invention concerns also the use of said emulsifying mixture as an emulsifying additive, in particular to create emulsions fuel/water, in which the fuel may be a biofuel, a vegetable oil, a diesel fuel or gasoline.
  • a further subject-matter of the invention is also a fuel/water emulsion comprising an emulsifier mixture according to the invention; preferably comprising an amount of emulsifier mixture equal to 0.1 -3.0 wt%, referred to the total emulsion weight.
  • the fuel is selected from the group consisting of a vegetable oil (e.g. rapeseed oil), a diesel and a gasoline.
  • a vegetable oil e.g. rapeseed oil
  • the emulsion contains preferably an amount of emulsifying mixture equal to 0.1 -0.3 wt% referred to the total emulsion weight.
  • the emulsion contains preferably an amount of emulsifying mixture equal to 0.8-1 .2 wt%, referred to the total emulsion weight.
  • the emulsion according to the invention is made by:
  • a fuel selected from the group consisting of a biofuel, a vegetable oil, a diesel fuel or gasoline;
  • the % given are % by weight referred to the total weight of the emulsion.
  • the amount of water is comprised between 10 and 25 wt%.
  • the emulsion process is carried out by way of fast stirring (rpm ranging between 2000 and 6000) within a vessel where all the components of the emulsion (oil, water and emulsifier) are placed.
  • the water used In order to obtain an emulsion that provides mechanical performances comparable to those of the pure fuel and does not cause damage to the engine, the water used must have a hardness comprised between 0 and 150 ° F.
  • the amount of water emulsifiable ranges from 1 to 35 wt% relative to the total weight; preferably from 5 to 30 wt%; still more preferably from 10 to 25 wt%.
  • the present invention will be better understood in the light of the following embodiments.
  • the component A is mixed with component B in a ratio of 70:30 wt%
  • the component A is mixed with component B in a ratio of 70:30 wt%
  • Example 3 Prepration of the emulsifier
  • the component A is mixed with component B in a ratio of 70:30 wt%
  • Example 4 Prepraration of an emulsified fuel
  • Example 5 Comparative test regarding the consumption of electrical motor generators
  • Fuel emulsion (75.5 wt% diesel, 22.5 wt% water, 2 wt% emulsifier) Electrical load supplied: 300 kW
  • Fuel consumption 1 15 L / h (of which 92 L/h are diesel)
  • Nitrogen oxides (mg/Nimc) 2097

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

La présente invention concerne un mélange émulsifiant à deux composants, pouvant être obtenu à partir de matières premières renouvelables. Le mélange émulsifiant susmentionné est particulièrement utile pour former des émulsions eau/carburant. Ces émulsions se sont avérées être stables pendant au moins 3 mois et ont montré qu'elles pouvaient être utilisées dans des dispositifs à combustion interne, sans modification substantielle du système mécanique ; pour obtenir des puissances de sortie du moteur alimenté par ces émulsions comparables à celles fournies lors de l'utilisation exclusive de carburant non émulsifié et pour obtenir des réduction significatives de la quantité de particules et de gaz à effet de serre émis par les fumées d'échappement.
PCT/IB2015/050490 2014-01-22 2015-01-22 Mélange émulsifiant et son utilisation Ceased WO2015110982A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITFI2014A000009 2014-01-22
ITFI20140009 2014-01-22

Publications (1)

Publication Number Publication Date
WO2015110982A1 true WO2015110982A1 (fr) 2015-07-30

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0812615A2 (fr) 1996-06-12 1997-12-17 Goro Ishida Procédé et appareil pour la préparation d'une émulsion combustible, un appareil pour la combustion d'un combustible émulsionné et un appareil pour alimentation en combustible émulsionné
WO1999063026A1 (fr) 1998-06-05 1999-12-09 Clean Fuels Technology, Inc. Compositions de carburant a haute stabilite
US20030196430A1 (en) 2000-06-20 2003-10-23 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
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
US20050039381A1 (en) * 2003-08-22 2005-02-24 Langer Deborah A. Emulsified fuels and engine oil synergy
EP1721956A2 (fr) 2000-01-12 2006-11-15 Pirelli & C. Ambiente Eco Technology S.p.A. Polymère tensioactif pour combustible comprenant une émulsion eau-huile
US20090260280A1 (en) * 2008-04-17 2009-10-22 Klausmeier William H Method of formulating a fuel composition for use in internal-combustion engines
CN102911749A (zh) 2012-10-30 2013-02-06 陕西启源科技发展有限责任公司 一种微乳化柴油及其制备方法
WO2013098630A1 (fr) 2011-12-29 2013-07-04 E.Fuel S.A. Émulsion de gasoil et d'eau

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0812615A2 (fr) 1996-06-12 1997-12-17 Goro Ishida Procédé et appareil pour la préparation d'une émulsion combustible, un appareil pour la combustion d'un combustible émulsionné et un appareil pour alimentation en combustible émulsionné
WO1999063026A1 (fr) 1998-06-05 1999-12-09 Clean Fuels Technology, Inc. Compositions de carburant a haute stabilite
EP1721956A2 (fr) 2000-01-12 2006-11-15 Pirelli & C. Ambiente Eco Technology S.p.A. Polymère tensioactif pour combustible comprenant une émulsion eau-huile
US20030196430A1 (en) 2000-06-20 2003-10-23 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
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
US20050039381A1 (en) * 2003-08-22 2005-02-24 Langer Deborah A. Emulsified fuels and engine oil synergy
US20090260280A1 (en) * 2008-04-17 2009-10-22 Klausmeier William H Method of formulating a fuel composition for use in internal-combustion engines
WO2013098630A1 (fr) 2011-12-29 2013-07-04 E.Fuel S.A. Émulsion de gasoil et d'eau
CN102911749A (zh) 2012-10-30 2013-02-06 陕西启源科技发展有限责任公司 一种微乳化柴油及其制备方法

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