EP1196514B1 - Melange de carburants aqueux - Google Patents

Melange de carburants aqueux Download PDF

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Publication number
EP1196514B1
EP1196514B1 EP00954505A EP00954505A EP1196514B1 EP 1196514 B1 EP1196514 B1 EP 1196514B1 EP 00954505 A EP00954505 A EP 00954505A EP 00954505 A EP00954505 A EP 00954505A EP 1196514 B1 EP1196514 B1 EP 1196514B1
Authority
EP
European Patent Office
Prior art keywords
weight
fuel mixture
fatty alcohols
emulsifiers
branched
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
Application number
EP00954505A
Other languages
German (de)
English (en)
Other versions
EP1196514A1 (fr
Inventor
Jürgen Röder
Frank Bongardt
Lothar Carl
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.)
BASF Personal Care and Nutrition GmbH
Original Assignee
Cognis Deutschland GmbH and Co KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Cognis Deutschland GmbH and Co KG filed Critical Cognis Deutschland GmbH and Co KG
Publication of EP1196514A1 publication Critical patent/EP1196514A1/fr
Application granted granted Critical
Publication of EP1196514B1 publication Critical patent/EP1196514B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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, 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
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C10L1/328—Oil emulsions containing water or any other hydrophilic phase

Definitions

  • the emulsifiers are contained in amounts of 0.5 to 26 wt .-%.
  • alcohols those having 1 to 8 carbon atoms are disclosed.
  • DE 37 09 195 A1 describes storage-stable aqueous fuel compositions which, in addition to hydrocarbons, contain a combination of 1.0 to 3.5% by weight of an emulsifier and 0.5 to 10% by weight of C 1-8 alcohols.
  • WO 85/04183 proposes aqueous propellants which contain 0.5 to 3.0% by weight of ethoxylated fatty alcohols having 12 to 14 C atoms as emulsifiers, although no concrete information on the degree of ethoxylation is given in the document.
  • the proposed aqueous propellants can on the one hand the increased Requirements for the emission limit values, on the other hand, the Presence of emulsifiers lead to engine malfunctions, e.g. for the formation of Deposits on the injectors or valves.
  • a first embodiment relates to a fuel mixture for internal combustion engines, containing fuels, water and emulsifiers, and optionally further additives, wherein as emulsifiers a mixture of (A) branched-chain, saturated or unsaturated fatty alcohols having 12 to 24 carbon atoms and (B) ethoxylated fatty alcohols with 8 to 24 carbon atoms and 1 to 10 moles of ethylene oxide per mole of fatty alcohol is included.
  • emulsifiers a mixture of (A) branched-chain, saturated or unsaturated fatty alcohols having 12 to 24 carbon atoms and (B) ethoxylated fatty alcohols with 8 to 24 carbon atoms and 1 to 10 moles of ethylene oxide per mole of fatty alcohol is included.
  • the fuel mixtures according to the invention contain 60 to 95 wt .-% of Fuel, 5 to 35% by weight of water, 0.01 to 5% by weight of emulsifiers (A) and (B) and 0 to 2.5% by weight of further additives.
  • fuel mixtures 65 to 90% by weight of a fuel, 25 to 35% by weight of water, 0.01 to 0.5% by weight of emulsifiers (A) and (B) and 0.01 to 0.5 wt .-% further additives.
  • fuels are all energy-supplying consumables, whose free combustion energy is converted into mechanical work, understood.
  • Motor fuels e.g. for car or truck engines, usually included Hydrocarbons, e.g. Gasoline or higher boiling petroleum fractions.
  • diesel fuels are made from gas oil by cracking or from tars, which in the smoldering of brown or Hard coal can be obtained. Common products have a density between 0.83 and 0.88 g / cc, a boiling point between 170 and 360 ° C and flash points between 70 and 100 ° C.
  • diesel and heating oils are preferred Fuels.
  • the Fuel / water mixtures according to the invention is the Water content, based on the mixture, at least 5 wt .-% and at most 35 wt .-%. Particularly preferred are those aqueous mixtures containing about 70 wt .-% of fuel and about 30 wt .-% water. These mixtures are then described below Emulsifier system added in the specified amounts.
  • the emulsifier components (A) and (B) are each known substance classes.
  • Fatty alcohols of component (A) are to be understood as meaning alcohols of the formula (I) R 1 OH in which R 1 is a branched chain saturated or branched chain unsaturated fatty alcohol having 12 to 24 carbon atoms and 0 and / or 1, 2 or 3 double bonds. Typical examples are isotridecyl, isohexadecyl, isostearyl or 2-hexyl-1-decanol alcohol and 2-octyldecanol, as well as their technical mixtures. Branched fatty alcohols of the type mentioned here can be obtained, for example, by customary processes, for example by oxo or Guerbet synthesis.
  • the products of the Guerbet syntheses which lead to alcohols uniformly branched in the ⁇ -position are preferred alcohols for the purposes of the present invention.
  • Particularly preferred are such fuels containing as component (A) branched, saturated fatty alcohols having 14 to 24 carbon atoms.
  • the compounds of component (B) are likewise known Compounds obtained by reaction of fatty alcohols of C chain length 12 to 18 with Received ethylene oxide under pressure and in the presence of acidic or alkaline catalysts become.
  • Suitable fatty alcohol ethoxylates contain from 1 to 10 moles per mole of fatty alcohol Ethylene oxide units.
  • fatty alcohols having 12 to 18 carbon atoms and 1 to 4 serve Mole of ethylene oxide per mole of fatty alcohol as starting materials for the ethoxylation.
  • suitable fatty alcohols include lauryl, myristyl, palmityl or stearyl alcohol.
  • suitable Unsaturated fatty alcohols are, for example, oleyl alcohol or 10-undecen-1-ol.
  • the amount of emulsifier components (A) and (B) used is in Sum preferably 0.01 to 5 wt .-%, in particular 0.01 to 2 wt .-% and especially preferably 0.01 to 1 wt .-%, based in each case on the amount of fuel and water.
  • the fuels may also contain other additives, preferably corrosion inhibitors, for example quaternary ammonium compounds or carboxamides and derivatives thereof. Particularly preferred is the concomitant use of ethoxylated carboxylic acid amides as corrosion inhibitors.
  • Such amides follow the general formula (II) R 2 -CO-NXR 3 in which R 2 is a saturated or unsaturated, linear or branched, optionally cyclic alkyl radical having 1 to 24 C atoms, X is a hydrogen atom or a methyl radical or a radical - (C 2 H 2 -O) n -H, and R 3 is a radical - (C 2 H 2 -O) n -H or a radical NY- (C 2 H 2 -O) m -H, where Y is a bivalent alkylene radical having 1 to 4 C atoms and n and m independently represent a number from 1 to 10.
  • the products of the formula (II) can be obtained by amidation of fatty acids or fatty acid mixtures and subsequent ethoxylation.
  • Suitable fatty acids are octane, decane, lauric, myristic, palmitic, stearic, behenic, arachic, oleic, erucic, ricinoleic acid or mixtures thereof, as used, for example, in coconut oil, palm oil, sunflower oil, safflower oil, Soybean oil, castor oil, whale oil, fish oil or tallow fat occur.
  • those amides are preferred which contain 12 to 24 carbon atoms and with 0.5 to 5 moles of ethylene oxide, preferably 1 to 3 moles of ethylene oxide per mole of carboxamide were reacted.
  • the emulsifier system according to the invention is added to the fuels in amounts of from 0.01 to a maximum of 5% by weight.
  • an additive package may be used, containing the components (A), (B) and optionally further auxiliaries, wherein the concentrate is free of water.
  • a further subject therefore relates to such anhydrous additive concentrates for aqueous fuels for internal combustion engines, containing branched-chain, saturated or unsaturated fatty alcohols having 12 to 24 carbon atoms, ethoxylated fatty alcohols having 8 to 24 carbon atoms and 1 to 10 moles of ethylene oxide per mole of fatty alcohol and ethoxylated carboxylic acid amides ,
  • These concentrates contain the emulsifier (A) in amounts of 10 to 30 wt .-%, the emulsifier (B) in amounts of 30 to 60 wt .-% and the ethoxylated carboxylic acid amides in amounts of 15 to 30 wt .-%.
  • Another object of the invention relates to a process for the preparation of aqueous Fuels wherein the aqueous fuels an additive concentrate according to the above Adds description to the fuel / water mixture in amounts of 0.01 to 5 wt .-%, preferably in amounts of from 0.01 to 2% by weight and in particular in amounts of from 0.01 to 1 Wt .-%.
  • An additive concentrate was prepared containing 20% by weight of 2-hexyl-1-decanol, 54 Wt% Oley / Cetyl alcohol x 2 EO and 26 wt% Tall oil fatty acid monoethanolamide x 1.5 EO, and this then to a mixture of 70 wt .-% diesel oil and 30 wt .-% water added.
  • the amount used of the additive concentrate was 0.1 wt .-%, based on the Amount of water and diesel. After brief stirring, a stable emulsion formed, which could easily be burned in a diesel generator.
  • the fuel / water mixtures according to the invention are suitable as fuels for internal combustion engines of all kinds, but preferably for diesel engines, in particular stationary diesel engines, as used for block power plants.
  • the fuels according to the invention it is possible to reduce the emission of soot and NO x below the current and future limits of the TA-air, without causing any impairment of the combustion process or the engine.
  • the fuel mixtures according to the invention are furthermore storage-stable, in particular at low temperatures, and can be obtained simply by mechanical mixing of the emulsifier system with the aqueous fuel.

Landscapes

  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (13)

  1. Mélange de carburant pour moteurs à combustion, contenant des hydrocarbures combustibles, de l'eau et des émulsifiants ainsi que, le cas échéant, d'autres additifs,
    caractérisé en ce que
    comme émulsifiants, il contient un mélange constitué
    (A) d'alcools gras saturés à chaíne ramifiée ou insaturés à chaíne ramifiée portant 12 à 24 atomes de C, et
    (B) d'alcools gras éthoxylés portant 8 à 24 atomes de C et 1 à 10 moles d'oxyde d'éthylène par mole d'alcool gras.
  2. Mélange de carburant selon la revendication 1,
    caractérisé en ce qu'
    il contient les émulsifiants (A) et (B) au total en quantité de 0,01 à 5 % en poids, de préférence de 0,01 à 2 % en poids et, en particulier de 0,01 à 1 % en poids.
  3. Mélange de carburant selon la revendication 1 ou 2,
    caractérisé en ce qu'
    il contient :
    a) 60 à 95 % en poids de carburant
    b) 5 à 35 % en poids d'eau
    c) 0,01 à 5 % en poids d'émulsifiants
    d) 0 à 2,5 % en poids d'autres additifs.
  4. Mélange de carburant selon les revendications 1 à 3,
    caractérisé en ce qu'
    il contient :
    a) 65 à 90 % en poids de carburant
    b) 25 à 35 % en poids d'eau
    c) 0,01 à 0,5 % en poids d'émulsifiants
    d) 0,01 à 0,5 % en poids d'autres additifs.
  5. Mélange de carburant selon les revendications 1 à 4,
    caractérisé en ce que
    le carburant est du gasoil.
  6. Mélange de carburant selon les revendications 1 à 5,
    caractérisé en ce que
    comme autres additifs, il contient des inhibiteurs de corrosion.
  7. Mélange de carburant selon les revendications 1 à 6,
    caractérisé en ce que
    les inhibiteurs de corrosion sont des amides d'acide carboxylique éthoxylés.
  8. Mélange de carburant selon les revendications 1 à 7,
    caractérisé en ce qu'
    il contient les émulsifiants (A) et (B) dans un rapport pondéral de 1 / 1 à 1/4.
  9. Mélange de carburant selon les revendications 1 à 8,
    caractérisé en ce que
    les émulsifiants (A) sont choisis dans le groupe des alcools gras ramifiés saturés portant 14 à 24 atomes de C.
  10. Mélange de carburant selon les revendications 1 à 9,
    caractérisé en ce que
    les émulsifiants (B) sont choisis dans le groupe des alcools gras éthoxylés portant 12 à 18 atomes de C et 1 à 4 moles d'oxyde d'éthylène par mole d'alcool gras.
  11. Concentré d'additifs pour carburants aqueux pour moteurs à combustion, contenant des alcools gras saturés à chaíne ramifiée ou insaturés à chaíne ramifiée portant 12 à 24 atomes de C, des alcools gras éthoxylés portant 8 à 24 atomes de C et 1 à 10 moles d'oxyde d'éthylène par mole d'alcool gras, et des amides d'acide carboxylique éthoxylés, ce concentré étant exempt d'eau.
  12. Concentré d'additifs selon la revendication 11,
    caractérisé en ce qu'
    il contient 10 à 30 % en poids d'alcools gras ramifiés, 30 à 60 % en poids d'alcools gras éthoxylés et 15 à 30 % en poids d'amides d'acide carboxylique éthoxylés, ce concentré étant exempt d'eau.
  13. Procédé de fabrication de carburants aqueux,
    caractérisé en ce qu'
    on ajoute aux carburants aqueux un concentré d'additifs selon les revendications 11 ou 12 en quantités de 0,01 à 5 % en poids.
EP00954505A 1999-07-23 2000-07-14 Melange de carburants aqueux Expired - Lifetime EP1196514B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19934689A DE19934689A1 (de) 1999-07-23 1999-07-23 Wäßriges Kraftstoffgemisch
DE19934689 1999-07-23
PCT/EP2000/006736 WO2001007541A1 (fr) 1999-07-23 2000-07-14 Melange de carburants aqueux

Publications (2)

Publication Number Publication Date
EP1196514A1 EP1196514A1 (fr) 2002-04-17
EP1196514B1 true EP1196514B1 (fr) 2005-03-30

Family

ID=7915875

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00954505A Expired - Lifetime EP1196514B1 (fr) 1999-07-23 2000-07-14 Melange de carburants aqueux

Country Status (7)

Country Link
EP (1) EP1196514B1 (fr)
AT (1) ATE292171T1 (fr)
AU (1) AU6693600A (fr)
CA (1) CA2380174A1 (fr)
DE (2) DE19934689A1 (fr)
ES (1) ES2239027T3 (fr)
WO (1) WO2001007541A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10115705A1 (de) * 2001-03-29 2002-10-10 Cognis Deutschland Gmbh Emulgatorenmischung für wässrige Dieselemulsionen
US6869706B2 (en) * 2002-01-25 2005-03-22 Exxonmobil Research And Engineering Company Alkoxylated alkyl ester and alcohol emulsion compositions for fuel cell reformer start-up
DE102007003344B3 (de) * 2006-12-15 2008-07-10 Helmut KÖRBER Dieselkraftstoffgemisch

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2653026A1 (de) * 1975-06-30 1978-05-24 Edward C Wenzel Als kraftstoff fuer verbrennungsmotoren verwendbares fluessigkeitsgemisch
BE793817A (fr) * 1972-01-11 1973-07-10 Texaco Ag Procede de production continue d'emulsions aqueuses de paraffine

Also Published As

Publication number Publication date
EP1196514A1 (fr) 2002-04-17
AU6693600A (en) 2001-02-13
CA2380174A1 (fr) 2001-02-01
ATE292171T1 (de) 2005-04-15
DE19934689A1 (de) 2001-01-25
ES2239027T3 (es) 2005-09-16
WO2001007541A1 (fr) 2001-02-01
DE50009927D1 (de) 2005-05-04

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