EP0681023B1 - Verträgliche Brennstoffzusatzkonzentrate - Google Patents

Verträgliche Brennstoffzusatzkonzentrate Download PDF

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Publication number
EP0681023B1
EP0681023B1 EP19950303035 EP95303035A EP0681023B1 EP 0681023 B1 EP0681023 B1 EP 0681023B1 EP 19950303035 EP19950303035 EP 19950303035 EP 95303035 A EP95303035 A EP 95303035A EP 0681023 B1 EP0681023 B1 EP 0681023B1
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Prior art keywords
fuel
accordance
concentrate
weight
groups
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Expired - Lifetime
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EP19950303035
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English (en)
French (fr)
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EP0681023A1 (de
Inventor
Charles Gareth Jeffrey
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Afton Chemical Ltd
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Afton Chemical Ltd
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    • C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
    • 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
    • C10L1/30—Organic compounds compounds not mentioned before (complexes)
    • C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
    • C10L1/303—Organic compounds compounds not mentioned before (complexes) derived from metals boron 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
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/30—Organic compounds compounds not mentioned before (complexes)
    • C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)

Definitions

  • Foam control is a highly important consideration in the preparation of additive compositions for use in fuels of the middle distillate boiling range, such as gas oils, diesel fuels, gas turbine fuels, burner fuels and the like. If a fuel foams during transfer from one tank to another, it becomes difficult to control flow rates and volumes. Similarly, foaming during the filling of fuel tanks can pose various other problems, such as delivery of inadequate amounts of fuel to the tanks or conversely, overflowing and spillage of fuel at the filling site.
  • foam inhibitors such as polyacrylates and polysiloxanes have been proposed for use in diesel fuels and additive packages to be used in formulating finished diesel fuels.
  • this invention provides in one of its embodiments an additive concentrate which comprises as components thereof (i) at least one overbased alkali or alkaline earth metal-containing detergent and (ii) a water-soluble polyether-polysiloxane copolymer having a siloxane backbone with organic poly(alkylene oxide) pendant groups attached to the siloxane backbone via direct silicon-to-carbon bonds. These copolymers also have hydrocarbyl pendant groups, preferably methyl groups, attached to the siloxane backbone via direct silicon-to-carbon bonds.
  • the weight ratio of (i) to (ii) on an active ingredient basis is normally in the range of 0.25 to 250 parts by weight of (i) per part by weight of (ii).
  • Another embodiment involves including in the above additive concentrate as a component thereof (iii) at least one hydrocarbon-soluble ashless dispersant, the weight ratio of (iii) to (ii) on an active ingredient basis being in the range of 0.25 to 300 parts by weight of (iii) per part by weight of (ii).
  • compositions of this invention are any of those described above wherein the concentrate further comprises as a component thereof (iv) at least one hydrocarbon-soluble cyclopentadienyl manganese tricarbonyl compound, the weight ratio of (iv) to (ii) on an active ingredient basis being in the range of 0.07 to 25 parts by weight of (iv) per part by weight of (ii).
  • liquid hydrocarbon diluent especially a liquid highly aromatic hydrocarbon diluent
  • liquid alcohol diluent especially a liquid alcohol diluent
  • demulsifying agent or a corrosion inhibitor especially a liquid alcohol diluent
  • Still other embodiments include liquid fuel compositions, such as fuels boiling in the middle distillate boiling range, containing the components in accordance with any of the foregoing additive concentrates.
  • the metal-containing detergents are exemplified by oil-soluble overbased salts of alkali or alkaline earth metals with one or more of the following acidic substances (or mixtures thereof): (1) sulfonic acids, (2) carboxylic acids, (3) salicylic acids, (4) alkylphenols, (5) sulfurized alkylphenols, (6) organic phosphorus acids characterised by at least one direct carbon-to-phosphorus linkage.
  • Such organic phosphorus acids include those prepared by the treatment- of an olefin polymer (e.g., polyisobutene having a molecular weight of 1000) with a phosphorizing agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphorothioic chloride.
  • a phosphorizing agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphorothioic chloride.
  • phosphorizing agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and
  • overbased is used to designate metal salts wherein the metal is present in stoichiometrically larger amounts than the organic acid radical.
  • the commonly employed methods for preparing the overbased salts involve heating a mineral oil solution of an acid with a stoichiometric excess of a metal neutralising agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide, carbonating the mixture in the presence of a promoter, and filtering the resulting mass.
  • a metal neutralising agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide
  • Examples of compounds useful as the promoter include phenolic substances such as phenol, naphthol, alkylphenol, thiophenol, sulfurized alkylphenol, and condensation products of formaldehyde with a phenolic substance; alcohols such as methanol, 2-propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol; and amines such as aniline, phenylenediamine, phenothiazine, phenyl- ⁇ -naphthylamine, and dodecylamine.
  • a particularly effective method for preparing the overbased salts comprises mixing an acid with an excess of a basic alkaline earth metal neutralising agent and at least one suitable promoter, and carbonating the mixture at an elevated temperature such as 60°-200°C.
  • overbased metal-containing phenate detergents include, but are not limited to, such substances as overbased lithium phenates, sodium phenates, potassium phenates, calcium phenates, magnesium phenates, sulfurized lithium phenates, sulfurized sodium phenates, sulfurized potassium phenates, sulfurized calcium phenates, and sulfurized magnesium phenates wherein each aromatic group has one or more aliphatic groups to impart hydrocarbon solubility.
  • overbased metal detergents are often referred to as "overbased" phenates or "overbased sulfurized phenates”.
  • overbased sulfonates examples include overbased lithium sulfonates, sodium sulfonates, potassium sulfonates, calcium sulfonates, and magnesium sulfonates wherein each sulfonic acid moiety is attached to an aromatic nucleus which in turn usually contains one or more aliphatic substituents to impart hydrocarbon solubility.
  • Overbased salicylate detergents are exemplified by lithium salicylates, sodium salicylates, potassium salicylates, calcium salicylates, and magnesium salicylates wherein the aromatic moiety is usually substituted by one or more aliphatic substituents to impart hydrocarbon solubility.
  • overbased lithium, sodium, potassium, calcium and magnesium salts of hydrolysed phospho-sulfurized olefins having 10 to 2000 carbon atoms or of hydrolysed phosphosulfurized alcohols and/or aliphatic-substituted phenolic compounds having 10 to 2000 carbon atoms; and (b) the overbased lithium, sodium, potassium, calcium and magnesium salts of aliphatic carboxylic acids and aliphatic-substituted cycloaliphatic carboxylic acids, this latter category often being referred to as "overbased carboxylates".
  • overbased alkali and alkaline earth metal salts of oil-soluble organic acids are suitable, such as the overbased aliphatic sulfonate salts, often referred to as "petroleum sulfonates", such as the overbased lithium, sodium, potassium, calcium and magnesium petroleum sulfonates.
  • mixtures of two or more different acids or two or more different types of acids e.g., one or more overbased calcium phenates with one or more overbased calcium sulfonates
  • acids e.g., one or more overbased calcium phenates with one or more overbased calcium sulfonates
  • barium salts While rubidium, cesium and strontium salts are feasible, their expense renders them impractical for most uses. Likewise, while barium salts are effective, the status of barium as a heavy metal under a toxicological cloud renders barium salts less preferred for present-day usage.
  • foam inhibitor used is of a makeup and type that does not exhibit the serious incompatibility with overbased metal detergents as is exhibited by a wide variety of siloxane-type foam inhibitors.
  • this invention utilizes certain water-soluble polyether-polysiloxane copolymers having poly(alkylene oxide) pendant groups attached to a siloxane backbone via carbon-to-silicon bonds.
  • water-soluble is meant that the copolymer is sufficiently soluble in water such that a clear water solution containing at least 15 weight percent of the copolymer can be formed at 25°C.
  • the polysiloxane backbone of the copolymer is also partially substituted by short chain hydrocarbyl groups such as methyl, ethyl or vinyl, most preferably methyl.
  • the preferred poly(alkylene oxide) pendant groups in the copolymer are poly(ethyleneoxy) groups or poly-co(ethyleneoxypropyleneoxy) groups which latter may have the -C 2 H 4 O- and -C 3 H 6 O- groups arranged randomly or in block sequences.
  • the propyleneoxy groups are branched chain groups in which an ethyleneoxy group is substituted with a pendant methyl group.
  • copolymers are the water-soluble copolymers of the formula where R is a short chain group (e.g., methyl, ethyl, propyl, vinyl), A is a poly(alkylene oxide) group in which the alkylene moieties are ethylene and/or propylene, and m and n are numbers such that the copolymer is water-soluble as defined above. Most preferably, the poly(alkylene oxide) groups have a terminal hydroxyl groups.
  • A is the group: -(CH 2 ) 3 -O-(C 2 H 4 O) x (C 3 H 6 O) y H
  • R is methyl
  • the polyalkylene oxide groups contain at least 60 weight percent ethyleneoxy moieties with the balance, if any, being propyleneoxy moieties. Copolymers in which the siloxane content falls in the range of 10 to 60 weight percent may be found suitable.
  • liquid polyether-polydimethylsiloxane copolymer having about 75 weight percent ethyleneoxy moieties and about 25 weight percent propyleneoxy moieties in the polyether portion of the copolymer, which polyether portions each terminate with a hydroxyl group.
  • products of this type in which the siloxane content is in the range of 25-35 weight percent are highly desirable.
  • the most preferred copolymer is TEGOPREN® 5851 silicone surfactant available from T.H. GOLDSCHMIDT AG, Essen, Germany.
  • This product is described as a diesel antifoam additive which is a polyether polymethylsiloxane copolymer having a siloxane content of about 30%, an ethyleneoxy/propyleneoxy content of 75:25, a terminal hydroxyl group on the polyether groups, a refractive index at 20°C of 1.450 ⁇ 0.005 and a cloud point in water at 1% concentration of 64 ⁇ 3 °C.
  • This product has a water solubility of well above 15 weight percent at 25°C.
  • compositions of at least one hydrocarbon-soluble ashless dispersant in proportions such as described above.
  • ashless dispersants comprise long chain succinimides, long chain succinic esters, long chain succinic ester-amides, long chain polyamines and long chain Mannich bases.
  • the long chain of these detergent-dispersants contains an average of at least 20 carbon atoms, e.g., an average of 30 to 200 or more carbon atoms.
  • Such long chain substituents are usually derived from polyolefin oligomers or polymers of suitable number average molecular weights such as about 800, 950, 1200, 1350, 1500, 1700, 2100 or 2300 which in turn are formed by polymerization or copolymerization of olefin monomers such as propylene, butylenes, isobutylene, amylenes, mixtures of ethylene and propylene, and the like.
  • One preferred group of dispersant-detergents for use in this invention are succinimides formed by reaction of a polyisobutenyl succinic anhydride and a polyamine, especially an ethylene polyamine having an average of 2 to 6 nitrogen atoms per molecule such as ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, and N-[2-hydroxyethyl)-ethylene diamine.
  • the polyisobutenyl group preferably has a GPC number average molecular weight in the range of 750 to 2300, more preferably 800 to 1350.
  • Mannich base dispersants formed by reaction of (i) an alkylphenol in which the alkyl group is derived from a olefin polymer that has a number average molecular weight in the range of 750 to 2300, preferably 800 to 1350 and most preferably 800 to 1100, (ii) polyalkylene polyamine and (iii) formaldehyde or a formaldehyde precursor.
  • the alkyl group of the alkylphenol is derived from polypropene having a number average molecular weight in the range of 800 to 1100
  • the polyalkylene polyamine is diethylene triamine.
  • Other useful dispersants are referred to, for example, in EP 476,196 B1.
  • compositions of this invention Materials which can be, and preferably are, included in the compositions of this invention are cyclopentadienyl manganese tricarbonyl compounds. Such compounds, when present in the finished fuels, contribute materially to reduction of exhaust emissions, particularly emission of particulates and smoke.
  • use of the cyclopentadienyl manganese tricarbonyl compounds in the compositions of this invention results in further improvements in induction system cleanliness, particularly cleanliness of inlet valves.
  • Cyclopentadienyl manganese tricarbonyl compounds which can be used in the practice of this invention include cyclopentadienyl manganese tricarbonyl, methylcyclopentadienyl manganese tricarbonyl, dimethylcyclopentadienyl manganese tricarbonyl, trimethylcyclopentadienyl manganese tricarbonyl, tetramethylcyclopentadienyl manganese tricarbonyl, pentamethylcyclopentadienyl manganese tricarbonyl, ethylcyclopentadienyl manganese tricarbonyl, diethylcyclopentadienyl manganese tricarbonyl, propylcyclopentadienyl manganese tricarbonyl, isopropylcyclopentadienyl manganese tricarbonyl, tert-butylcyclopentadienyl manganese tricarbonyl, octylcyclopenta
  • cyclopentadienyl manganese tricarbonyls which are liquid at room temperature such as methylcyclopentadienyl manganese tricarbonyl, ethylcyclopentadienyl manganese tricarbonyl, liquid mixtures of cyclopentadienyl manganese tricarbonyl and methylcyclopentadienyl manganese tricarbonyl, mixtures of methylcyclopentadienyl manganese tricarbonyl and ethylcyclopentadienyl manganese tricarbonyl, etc. Preparation of such compounds is described in the literature, for example, U.S. 2,818,417.
  • manganese oleate manganese naphthenates
  • manganese octylacetoacetate manganese ethylene diamine tetracetate
  • compositions of this invention may be included in various other suitable components. Typical materials that may be so included are identified below.
  • Liquid hydrocarbon diluents Liquid hydrocarbon diluents .
  • Various liquid hydrocarbons such as those boiling in the middle distillate boiling range, can be used as diluents.
  • hydrocarbons enriched in cycloaliphatic or aromatic hydrocarbons are preferred.
  • Aromatic hydrocarbons such as toluene, xylene, and mixtures such as aromatic naphthas boiling in the range of 160 to 300°C and having a viscosity in the range of 1.4 to 3.0 cSt at 25°C are highly suitable materials.
  • Liquid alcohol diluents Any alcohol that is fuel-soluble and liquid at ambient room temperatures can be used as diluents. Preferred are liquid fuel-soluble alkanols having in the range of 5 to 13 carbon atoms per molecule. Most preferred are liquid branched chain primary alkanols having 7 to 13 carbon atoms in the molecule or blends of alcohols containing a major amount of one or more such branched chain primary alkanols.
  • Demulsifying agents A wide variety of demulsifiers are available for use in the practice of this invention, including, for example, polyoxyalkylene glycols, oxyalkylated phenolic resins, and like materials. Particularly preferred are mixtures of polyoxyalkylene glycols and oxyalkylated alkylphenolic resins, such as are available commercially from Petrolite Corporation under the TOLAD trademark.
  • One such proprietary product, identified as TOLAD 9310 is understood to be a mixture of these components dissolved in a solvent composed of heavy aromatic naphtha and isopropanol. This product has been found efficacious for use in the compositions of this invention.
  • other known demulsifiers can be used such as TOLAD 286K and OFRIC D5021 available commercially from Baker Performance Chemical (a division of Baker Hughes Limited).
  • Corrosion inhibitors a variety of materials are available for use as corrosion inhibitors in the practice of this invention.
  • dimer and-trimer acids such as are produced from tall oil fatty acids, oleic acid, linoleic acid, or the like. Products of this type are currently available from various commercial sources, such as, for example, the dimer and trimer acids sold under the HYSTRENE trademark by the Humko Chemical Division of Witco Chemical Corporation and under the EMPOL trademark by Emery Chemicals.
  • alkenyl succinic acid and alkenyl succinic anhydride corrosion inhibitors such as, for example, dodecenylsuccinic acid, dodecenylsuccinic anhydride, tetrapropenylsuccinic acid, tetrapropenylsuccinic anhydride, tetradecenylsuccinic acid, tetradecenylsuccinic anhydride, hexadecenylsuccinic acid, and hexadecenylsuccinic anhydride.
  • dodecenylsuccinic acid dodecenylsuccinic anhydride
  • tetrapropenylsuccinic acid tetrapropenylsuccinic anhydride
  • tetradecenylsuccinic acid tetradecenylsuccinic anhydride
  • hexadecenylsuccinic acid hexade
  • each of R 2 , R 3 , R 5 and R 6 is, independently, a hydrogen atom or a hydrocarbyl group containing 1 to 30 carbon atoms
  • each of R 1 and R 4 is, independently, a hydrogen atom, a hydrocarbyl group containing 1 to 30 carbon atoms, or an acyl group containing from 1 to 30 carbon atoms.
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 when in the form of hydrocarbyl groups can be, for example, alkyl, cycloalkyl or aromatic containing groups.
  • R 1 , R 2 , R 3 , R 4 and R 5 are hydrogen or the same or different straight-chain or branched-chain hydrocarbon radicals containing 1-20 carbon atoms.
  • R 1 , R 2 , R 3 , R 4 , and R 5 are hydrogen atoms.
  • R 6 when in the form of a hydrocarbyl group is preferably a straight-chain or branched-chain saturated hydrocarbon radical.
  • This type of corrosion inhibitor is a tetraalkenyl succinic acid of the above formula wherein R 1 , R 2 , R 3 , R 4 and R 5 are hydrogen and R 6 is a tetrapropenyl group.
  • Preferred corrosion inhibitors for use in this invention are low molecular weight succinimide/amide of polyalkylene polyamine.
  • One commercially-available material of this type is HITEC® 536 corrosion inhibitor (Ethyl Petroleum Additives Limited). Also preferred are neutral corrosion inhibitors some of which are available under the HiTEC trademark.
  • Carrier fluids There are various types of material useful as agents to assist in transporting additives of low volatility into the engine. These include mineral oils, poly- ⁇ -olefin oligomer fluids (hydrogenated or unhydrogenated), polyoxyalkylene glycols, polyoxyalkylene glycol ethers, polyoxyalkylated phenols, long chain ester fluids, and similar materials. Mixtures of two or more different carrier fluids can also be used. Typically the carrier fluids have viscosities of up to 10 cSt at 100°C.
  • phenolic antioxidants are generally among the more preferred materials. These include mononuclear monohydric phenols and alkylene bridged alkylphenols. Preferably, these fuel-soluble phenolic antioxidants have from 10 to 30 carbon atoms per molecule and are sterically hindered.
  • Suitable materials include 2-tert-butylphenol, 2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol,2,4-dimethyl-6-tert-butylphenol, N-(3,5-di-tert-butyl-4-hydroxybenzyl)-N.N-dimethylamine, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol),4,4'-methylenebis(2,6-di-tert-butylphenol), and mixed sterically-hindered methylene bridged polyalkylphenols.
  • Metal deactivators Generally speaking, metal deactivators fall into two broad categories. One category comprises the passivators which are considered to react with the metal surface and thereby passivate the surface. The other category comprises the chelators, i.e., substances which have the capability of reacting or complexing with dissolved metal and/or metal ions.
  • An example of the passivator type is the thiadiazoles such as HITEC 314 additive (Ethyl Petroleum Additives, Ltd.; Ethyl Petroleum Additives, Inc.).
  • Examples of the chelator type of metal deactivators include 8-hydroxyquinoline, ethylene diamine tetracarboxylic acid, ⁇ -diketones such as acetylacetone, ⁇ -ketoesters such as octyl acetoacetate, and the like.
  • the preferred metal deactivators which are generally regarded as chelators, are Schiff bases, such as N,N'-disalicylidene-1,2-ethanediamine, N,N'-disalicylidene-1,2-propanediamine, N,N'-disalicylidene-1,2-cyclohexanediamine, and N,N"-disalicylidene-N'-methyl-dipropylenetriamine.
  • Schiff bases such as N,N'-disalicylidene-1,2-ethanediamine, N,N'-disalicylidene-1,2-propanediamine, N,N'-disalicylidene-1,2-cyclohexan
  • a particular advantage associated with the use of the metal deactivators, especially of the Schiff base chelator type, is their ability to overcome instability caused in certain hydrocarbonaceous base fuels by the presence of typical manganese carbonyl compounds such as the cyclopentadienyl manganese tricarbonyls in combination with typical metal detergents.
  • the most preferred metal deactivators of this type are N,N'-disalicylidene-1,2-alkanediamines and N,N'--disalicylidene-1,2-cycloalkanediamines, especially N,N'-disalicylidene-1,2-propanediamine. Mixtures of metal deactivators can be used.
  • Wax antideposition or wax inhibitor additives Some additives or additive mixtures have the property of either preventing deposition of wax and/or inhibiting the formation of wax. Such additive compositions can also be used in the fuels of this invention. Illustrative materials are described for example in EP 153,176.
  • the advantages of this invention may be achieved in any liquid fuel derived from petroleum, biomass, coal, shale and/or tar sands.
  • the base fuels will be derived primarily, if not exclusively, from petroleum.
  • the invention is thus applicable to such fuels as kerosene, jet fuel, aviation fuel, diesel fuel, home heating oil, light cycle oil, heavy cycle oil, light gas oil, heavy gas oil, bunker fuels, residual fuel oils, ultra heavy fuel oils, and in general, any liquid (or flowable) product suitable for combustion either in an engine (e.g., diesel fuel, gas turbine fuels, etc.) or in a burner apparatus (e.g., gas oils, inland heavy fuel oil, residual fuel oils, visbreaker fuel oils, home heating oils, etc.).
  • an engine e.g., diesel fuel, gas turbine fuels, etc.
  • a burner apparatus e.g., gas oils, inland heavy fuel oil, residual fuel oils, visbreaker fuel oils, home heating oils, etc.
  • suitable fuels may include liquid fuels derived from biomass, such as vegetable oils (e.g., rapeseed oil, jojoba oil, cottonseed oil, etc.); or refuse-derived liquid fuels such as fuels derived from municipal and/or industrial wastes; or waste oils and/or liquid waste biomass and its derivatives; or mixtures of any of the foregoing substances.
  • vegetable oils e.g., rapeseed oil, jojoba oil, cottonseed oil, etc.
  • refuse-derived liquid fuels such as fuels derived from municipal and/or industrial wastes; or waste oils and/or liquid waste biomass and its derivatives; or mixtures of any of the foregoing substances.
  • the components of the additive compositions are employed in the fuels in minor amounts sufficient to improve the combustion characteristics and properties of the base fuel in which they are employed.
  • the amounts will thus vary in accordance with such factors as base fuel type and service conditions for which the finished fuel is intended.
  • concentrations (ppm) of the components (active ingredients) in the base fuels are illustrative: General Range Preferred Range Particularly Preferred Range Component i) 10 - 250 15 - 150 40 - 110 Component ii) 1 - 40 5 - 25 8 - 20
  • the individual components i) and ii), and also iii) and/or iv) (if used), can be separately blended into the fuel or can be blended therein in various subcombinations, if desired.
  • the particular sequence of such blending steps is not critical.
  • such components can be blended in the form of a solution in a diluent. It is preferable, however, to blend the components used in the form of an additive concentrate of this invention, as this simplifies the blending operations, reduces the likelihood of blending errors, and takes advantage of the compatibility and solubility characteristics afforded by the overall concentrate.
  • the additive concentrates of this invention will contain components i) and ii), and optionally, but preferably, one or more of components iii) and iv), in amounts proportioned to yield fuel blends consistent with the concentrations tabulated above.
  • the additive concentrate will contain one or more diluents such as light mineral oils, to facilitate handling and blending of the concentrate.
  • concentrates containing up to 90% by weight of one or more diluents or solvents are frequently used.
  • Antifoam Agent Description A Water-soluble polyether-polysiloxane copolymer having a siloxane backbone with organic polyalkylene oxide pendant groups and methyl groups attached to the siloxane backbone via direct silicon to carbon bonds - Tegopren 5851 (TH.
  • Antifoam agent A represents a material that meets the requirements for use in the practice of this invention whereas the other antifoam agents do not comply with the requirements of this invention.
  • the antifoam agent-free additive package was composed of 33% of a commercial overbased calcium alkylbenzene sulfonate which has a nominal TBN of 300 (HiTEC® 611 additive; Ethyl Petroleum Additives Limited), 4.5% of a 62% solution of methylcyclopentadienyl manganese tricarbonyl in light petroleum naphtha, 13.12% of a polyisobutenyl succinimide ashless dispersant (HiTEC® 9645 additive; Ethyl Petroleum Additives Limited), 0.95% of rust inhibitor (HiTEC® 536 additive; Ethyl Petroleum Additives Limited), 1.0% of demulsifying agent (OFRIC D5021; Baker Performance Chemical), and 47.43% of isodecanol.
  • HiTEC® 611 additive Ethyl Petroleum Additives Limited
  • HiTEC® 9645 additive Ethyl Petroleum Additives Limited
  • HiTEC® 536 additive Ethyl Petroleum Additives Limited
  • demulsifying agent O
  • the base fuel used in all tests was a commercially-available additive-free diesel fuel having a sulfur content of about 0.3% by weight. This fuel had the following distillation profile when subjected to the IP 123 test procedure: Initial boiling point 177.9°C 10% distillation point 236.4°C 50% distillation point 278.9°C 90% distillation point 355.9°C The fuel had an aromatics content of 29.53% as determined by the IP 391 procedure.
  • measured quantities of different antifoam agents were added to separate portions of the antifoam agent-free additive concentrate and the resultant additive concentrates were then promptly blended into the base fuel to produce fuel compositions which in each case contained an amount of the additive concentrate equivalent to 400 parts per million by volume (ppm v/v) of the antifoam agent-free additive package along with a specified amount of the antifoam agent which had been included in the package.
  • the respective fuels were then promptly shaken under controlled conditions, and in each instance the time needed for the foam to dissipate was measured.
  • Runs 13-15 show that the concentrates and fuels of this invention retained their effectiveness in foam suppression for as long as 39 days.
  • Table 3 summarizes the materials used and the results.
  • the numerical values for the components represent the relative proportions of the components, the treat rates are expressed in terms of ppm v/v, the times are expressed in terms of minutes and seconds in duplicate runs and represent the times required for the foam to dissipate, and the above components of the concentrate are identified as follows:
  • SILWET® L-7604, L-7607, L-7600, L-7605, and L-7200 Surfactants (Union Carbide Corporation).

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Claims (15)

  1. Additivkonzentrat, umfassend als Bestandteile (i) mindestens ein überbasisches Alkali oder Erdalkali enthaltendes Detergenz und (ii) ein wasserlösliches Polyether-Polysiloxan-Copolymerisat, das ein Siloxangerüst mit Hydrocarbylgruppen und über direkte Silicium-Kohlenstoff-Bindungen am Siloxangerüst hängende organische Polyalkylenoxid-Seitengruppen aufweist, wobei das Gewichtsverhältnis von (i) zu (ii) auf Basis aktiver Bestandsteile im Bereich von 0,25 zu 250 Gewichtsteilen (i) pro Gewichtsteil (ii) beträgt.
  2. Konzentrat nach Anspruch 1, das weiterhin als Bestandteil (iii) mindestens ein kohlenwasserstofflösliches aschefreies Dispergiermittel aufweist, wobei das Gewichtsverhältnis von (iii) zu (ii) auf Basis aktiver Bestandteile im Bereich von 0,25 zu 300 Gewichtsteilen (iii) pro Gewichtsteil (ii) beträgt.
  3. Konzentrat nach Anspruch 1 oder Anspruch 2, das weiterhin als Bestandteil (iv) mindestens eine kohlenwasserstofflösliche Cyclopentadienylmangantricarbonylverbindung umfasst, wobei das Gewichtsverhältnis (iv) zu (ii) auf Basis aktiver Bestandteile im Bereich von 0,07 bis 25 Gewichtsteile (iv) pro Gewichtsteil (ii) beträgt.
  4. Konzentrat nach einem der vorstehenden Ansprüche, das weiterhin als Bestandteil(e) ein Kohlenwasserstoffverdünnungsmittel oder ein alkoholisches Verdünnungsmittel oder deren Gemische aufweist.
  5. Konzentrat nach einem der vorstehenden Ansprüche, das weiterhin als Bestandteil(e) ein Demulgierungsmittel oder ein Rostschutzmittel oder deren Gemische aufweist.
  6. Konzentrat nach einem der vorstehenden Ansprüche, worin (i) mindestens ein Alkali- oder Erdalkalisulfonat mit einer Gesamtbasenzahl von mindestens 200 umfasst.
  7. Konzentrat nach Anspruch 6, wobei das Sulfonat ein Calciumalkylbenzolsulfonat mit einer Gesamtbasenzahl oberhalb von 250 ist.
  8. Konzentrat nach einem der vorstehenden Ansprüche, wobei (ii) ein Polyether-Polydimethylsiloxan-Copolymerisat ist, in dem die Polyalkylenoxid-Seitengruppen aus Ethylenoxid und Propylenoxid in einem Gewichtsverhältnis von etwa 75 % -(C2H4O)-Gruppen und etwa 25 % -(C3H6O)-Gruppen bestehen und das Copolymerisat einen Siloxangehalt von etwa 30 Gew.-% aufweist.
  9. Flüssiger Treibstoff, enthaltend Bestandteile gemäß einem der Ansprüche 1 bis 8.
  10. Treibstoff nach Anspruch 9, wobei der Treibstoff ein im Mitteldestillat-Bereich siedender Treibstoff ist.
  11. Treibstoff nach Anspruch 9 oder 10, der zusätzlich ein Antioxidans enthält.
  12. Treibstoff nach einem der Ansprüche 9 bis 11, der zusätzlich ein Mittel zur Verbesserung der Kaltfließfähigkeit aufweist.
  13. Treibstoff nach einem der Ansprüche 9 bis 12, der Dieseltreibstoff ist.
  14. Treibstoff nach Anspruch 13, der zusätzlich einen Verbesserer der Cetanzahl enthält.
  15. Treibstoff nach Anspruch 14, wobei der Verbesserer der Cetanzahl ein organisches Nitrat ist.
EP19950303035 1994-05-04 1995-05-03 Verträgliche Brennstoffzusatzkonzentrate Expired - Lifetime EP0681023B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9408814A GB2289287A (en) 1994-05-04 1994-05-04 Fuel foam control additive
GB9408814 1994-05-04

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Publication Number Publication Date
EP0681023A1 EP0681023A1 (de) 1995-11-08
EP0681023B1 true EP0681023B1 (de) 2000-03-01

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DE (1) DE69515196D1 (de)
GB (1) GB2289287A (de)
HK (1) HK1002223A1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE59709623D1 (de) * 1996-12-17 2003-04-30 Goldschmidt Ag Th Verwendung von Silicon-Polyether-Copolymeren zum Entschäumen von Dieselkraftstoff
GB2322138A (en) * 1997-02-17 1998-08-19 Ethyl Petroleum Additives Ltd Foam reducing fuel additive
CN1101238C (zh) * 1998-01-21 2003-02-12 辽河石油勘探局勘察设计研究院 一种原油破乳剂及其制备方法
US6200359B1 (en) * 1998-12-23 2001-03-13 Shell Oil Company Fuel oil composition
AU1420600A (en) 1999-09-06 2001-04-10 Agrofuel Ab Motor fuel for diesel engines
US6514297B1 (en) * 1999-11-24 2003-02-04 The Lubrizol Corporation Detergents for use in preventing formation of iron complexes in hydrocarbon fuels
FR2839315B1 (fr) * 2002-05-03 2006-04-28 Totalfinaelf France Additif pour ameliorer la stabilite thermique de compositions d'hydrocarbures
US20050005506A1 (en) * 2003-07-08 2005-01-13 Henly Timothy J. Distillate fuel compositions for improved combustion and engine cleanliness
US20120222348A1 (en) * 2011-03-01 2012-09-06 Basf Se Medium-chain alkanols in additive concentrates for improving foam reduction in fuel oils
WO2012117004A2 (de) 2011-03-01 2012-09-07 Basf Se Mittelkettige alkanole in additivkonzentraten zur verbesserung der schaumreduktion in brennstoffölen

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Publication number Priority date Publication date Assignee Title
DE2861399D1 (en) * 1977-08-04 1982-01-28 Exxon Research Engineering Co Overbased monoalkyl orthoxylene and monoalkyl toluene sulfonates and use as lubricant additives
US4428850A (en) * 1982-01-28 1984-01-31 Texaco Inc. Low foaming railway diesel engine lubricating oil compositions
US4460380A (en) * 1982-12-27 1984-07-17 Exxon Research & Engineering Co. Water shedding agents in distillate fuel oils
NO168054C (no) * 1985-03-29 1992-01-08 Dow Corning Polysiloksan-polyoksyalkylen-kopolymer som antiskummiddeltil diesel og flybensin.
GB8508254D0 (en) * 1985-03-29 1985-05-09 Dow Corning Ltd Foam control
DE69004692T2 (de) * 1990-09-20 1994-03-10 Ethyl Petroleum Additives Ltd Kohlenwasserstoffzusammensetzungen und Zusätze dafür.
EP0529161A1 (de) * 1991-08-23 1993-03-03 Ethyl Petroleum Additives, Inc. Erhöhte schaumhemmende Eigenschaften besitzende Schmiermittel und funktionelle Flüssigkeiten
GB9122158D0 (en) * 1991-10-18 1991-11-27 Exxon Chemical Patents Inc Fuel oil compositions
GB9315205D0 (en) * 1993-07-22 1993-09-08 Exxon Chemical Patents Inc Additives and fuel compositions

Also Published As

Publication number Publication date
GB2289287A (en) 1995-11-15
EP0681023A1 (de) 1995-11-08
GB9408814D0 (en) 1994-06-22
HK1002223A1 (en) 1998-08-07
DE69515196D1 (de) 2000-04-06

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