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
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
• • 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
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
  • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
• • 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
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
• • 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
  • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
  • C10L1/2493—Organic compounds containing sulfur, selenium and/or tellurium compounds of uncertain formula; reactions of organic compounds (hydrocarbons, acids, esters) with sulfur or sulfur containing compounds

Definitions

• This invention relates to fuel oils which exhibit improved conductivity properties and an additive system for providing such properties
• U.S. Patent 6,391,070, issued May 21,2002 to Schield discloses a composition having increased electrical conductivity, which includes a) a liquid hydrocarbon; b) an anti-static amount of at least one hydrocarbon soluble copolymer of an alkylvinyl monomer and a cationic vinyl monomer, wherein the copolymer has an alkylvinyl monomer unit to cationic vinyl monomer unit ratio of from about 1:1 to about 10:1, the copolymer having an average molecular weight of from about 800 to about 1,000,000; and c) an anti-static amount of at least one hydrocarbon soluble polysulfone copolymer of at least one olefin and sulfur dioxide.
• These polymers are described by Schield in U. S. Patent 5,672,183 as containing a cationic quaternary ammonium monomer.
• the present invention is based upon the discovery that the use in combination of an acrylate, methacrylate or fumarate polymer, not prepared from a cationic quaternary ammonium monomer, with certain commercial conductivity improvers results in a synergistic effect upon the conductivity properties of a fuel oil having little or no inherent conductivity.
• the invention is particularly useful for the formulation of turbine combustion fuel oils which are generally those hydrocarbon fuels having boiling ranges within the limits of about 150° to 600°F and are designated by such terms as JP-4, JP-5, JP-7, JP-8, Jet A, Jet A-1.
• JP-4 and JP-5 are fuels defined by U.S. military specification MIL-T-5624-N and JP-8 is defined by U.S. Military Specification MIL-T83133-D. Jet A, Jet A-1 and Jet B are defined by ASTM specification D1655.
• a fuel oil composition which comprises a fuel oil having an inherent conductivity of less than 10 pS/m containing a two component additive comprising:
• Suitable polyacrylate, polymethacrylate or polyfumarate polymers are those polymers of ethylenically unsaturated monomers such as methacrylic, acrylic or fumaric acid esters of alcohols having about 1 to 40 carbon atoms, such as methylacrylate, ethylacrylate, n-propylacrylate, lauryl acrylate, stearyl acrylate, methylmethacrylate, ethylmethacrylate, n-propylmethacrylate, lauryl methacrylate, stearyl methacrylate and the like.
• These polymers may have number average molecular weights (Mn) of 1,000 to 10,000,000 and preferably the molecular weight range is from about 10,000 to 1,000,000, most preferably 10,000 to 100,000. These polymers do not include copolymers with quaternary ammonium acrylate monomers such as disclosed in U.S. Patent 5, 672, 183.
• the acrylate, methacrylate or fumarate monomer is copolymerized with an amine-containing or amide-containing monomer (excluding quaternary ammonium monomers), or the acrylate or methacrylate main chain polymer is provided so as to contain sites suitable for grafting, and then amine-containing or amide-containing branches, either monomers or macromonomers, (but excluding quaternary ammonium monomers or macromonomers), are grafted onto the main chain. Transesterification reactions or amidation reactions may also be employed to produce the same products.
• the polymer will contain 0.4 to 4.0 wt.% nitrogen.
• Particularly preferred is a polymer of methacrylate of C 8 -C 14 alcohols copolymerized with a methacrylamide of an (N,N-dialkylamino)alkylamine, such as dimethylaminopropylamine.
• the weight average molecular weight of the polysulfone will be in the range of 10,000 to 1,500,000 with the preferred range being 50,000 to 900,000 and the most preferred molecular weight range being in the range of about 100,000 to 500,000.
• the olefins useful for the preparation of the polysulfones may have about 6 to 20 carbon atoms, preferably about 6 to 18 carbon atoms, with 1-decene polysulfone being particularly preferred.
• the preparation of these materials is known in the art as described for example in U.S. Patent 3,917,466.
• the polymeric polyamine component is prepared by heating an amine with epichlorohydrin in the molar proportions of 1:1 to 1:1.5 in the range of 50°C to 100°C.
• Suitable aliphatic primary amines will have about 8 to 24 carbon atoms, preferably about 8 to 12 carbon atoms, with the aliphatic group being preferably an alkyl group. If the amine used is an N-aliphatic hydrocarbyl alkylene diamine, the aliphatic hydrocarbyl group will have 8 to 24 carbon atoms and will preferably be alkyl and the alkylene group will have 2 to 6 carbon atoms.
• the preferred N-aliphatic hydrocarbyl alkylene diamine is N-aliphatic hydrocarbyl 1,3-propylenediamine which are commercially available.
• a preferred commercially available polymeric polyamine is believed to be the polymeric reaction product of N-tallow-1,3-propylenediamine with epichlorohydrin sold as "Polyflo 130" sold by Universal Oil Co.
• the polymeric polyamine reaction product will have a degree of polymerization of about 2 to 20. The description of these materials is also disclosed in U.S. Patent 3,917,466.
• the polymeric polyamine reaction product component will be used in the form of a sulfonic acid salt.
• a sulfonic acid salt Useful are oil soluble sulfonic acids such as alkane sulfonic acid or an aryl sulfonic acid. Particularly suitable is dodecyl benzene sulfonic acid.
• the hydrocarbon soluble copolymer of an alkylvinyl monomer and a cationic vinyl monomer is described in and may be made by the procedures of U.S. Patent No. 5,672,183, the entirety of which is incorporated by reference herein.
• the copolymer has an alkylvinyl monomer unit to cationic vinyl monomer unit ratio of from 1:1 to about 10:1, the copolymer having a number average molecular weight of from about 800 to about 1,000,000.
• the cationic vinyl monomer is a cationic quaternary ammonium vinyl monomer, and in a preferred embodiment is a cationic quaternary ammonium acrylate monomer or a cationic quaternary ammonium methacrylate monomer.
• a copolymer of an alkyl vinyl monomer and a nitrile-containing monomer may be used in conjunction with the copolymer of alkylvinyl monomer and cationic vinyl monomer.
• the components of the conductivity-improving additive according to the invention are present in the fuel oil composition in an amount effective to improve conductivity.
• the polyacrylate, polymethacrylate or polyfumarate materials are preferably used in the compositions of the present invention in amounts ranging from 5 - 400 ppm, more preferably about 10 - 160 ppm (by weight).
• the polysulfonic-polyamine mixture conductivity improver or the alkylvinyl monomer-cationic vinyl monomer copolymer conductivity improver may each be used in amounts from 0.25-2 ppm, preferably about 0.35-1 ppm.
• compositions of this invention may also contain an antioxidant compound.
• the amount of antioxidant compound incorporated may vary over a range of about 1 - 100 ppm, preferably about 10 - 50 ppm, such as about 25 ppm by weight.
• the antioxidant compound is a phenolic antioxidant compound.
• the preferred phenolic antioxidant compounds are the hindered phenolics which are those which contain a sterically hindered hydroxyl group. These include those derivatives of dihydroxy aryl compounds in which the hydroxyl groups are in the ortho- or para- position to each other.
• Typical phenolic antioxidants include the hindered phenols substituted with alkyl groups of a total of 6 or more carbon atoms and the alkylene coupled derivatives of these hindered phenols.
• phenolic materials of this type are 2,6-di-t-butyl-4-methyl phenol (BHT, butylated hydroxy toluene); 2-t-butyl-4-heptyl phenol; 2-t-butyl-4-octyl phenol; 2-t-butyl-4-octyl phenol; 2-t-butyl-4-dodecyl phenol; 2,6-di-t-butyl-4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl phenol; 2-methyl-6-di-t-butyl-4-heptyl phenol; and 2-methyl-6-di-t-butyl-4-dodecyl phenol.
• BHT butylated hydroxy toluene
• 2-t-butyl-4-heptyl phenol 2-t-butyl-4-octyl phenol
• 2-t-butyl-4-octyl phenol
• ortho coupled phenols examples include 2,2'-bis(6-t-butyl-4-heptyl phenol); 2,2'-bis(6-t-butyl-4-octyl phenol); and 2,2'-bis(6-t-butyl-4-dodecyl phenol).
• Sulfur containing phenols can also be used. The sulfur can be present as either aromatic or aliphatic sulfur within the phenolic antioxidant molecule.
• BHT is especially preferred, as are 2,6- and 2,4-di-t-butylphenol and 2,4,5- and 2,4,6-triisopropylphenol, especially for use in jet fuels.
• compositions will preferably contain about 0.1 - 50 ppm of a metal deactivator, preferably 1 - 10 ppm by weight.
• a metal deactivator preferably 1 - 10 ppm by weight.
• suitable metal deactivators are:
• the fuel oil compositions of this invention may also contain one or more other additives commonly employed in fuels present in such amounts so as to provide their normal attendant functions.
• cold flow improvers such as ethylene-unsaturated ester copolymers, comb polymers containing hydrocarbyl groups pendant from a polymer backbone, polar nitrogen compounds, compounds having a cyclic ring system having at least two substituents of the formula -A-NR 15 R 16 where A is linear or branched hydrocarbylene and R 15 and R 16 are C 9 -C 40 hydrocarbyl, hydrocarbon polymers such as ethylene alpha-olefin copolymers, polyoxyethylene esters, ethers and ester/ether mixtures such as behenic diesters of polyethylene glycol.
• additives include lubricity additives such as fatty acids, dimers of fatty acids, esters of fatty acids or dimers of fatty acids, corrosion inhibitors, anti-icing additives such as ethylene glycol monomethyl ether or diethylene glycol monomethyl ether, biocides, thermal stability additives, anti-rust agents, anti-foam agents, demulsifiers, detergents, dispersants, cetane improvers, stabilisers, antioxidants, static dissipator additives and the like.
• lubricity additives such as fatty acids, dimers of fatty acids, esters of fatty acids or dimers of fatty acids, corrosion inhibitors, anti-icing additives such as ethylene glycol monomethyl ether or diethylene glycol monomethyl ether, biocides, thermal stability additives, anti-rust agents, anti-foam agents, demulsifiers, detergents, dispersants, cetane improvers, stabilisers, antioxidants, static dissipator additives and the like.
• the fuel oil may be a hydrocarbon fuel such as a petroleum-based fuel oil for example gasoline, kerosene or distillate fuel oil.
• the fuel oil can comprise atmospheric distillate or vacuum distillate, or cracked gas oil or a blend in any proportion of straight run and thermally and/or catalytically cracked distillates.
• the most common petroleum distillate fuels are kerosene, jet fuels, diesel fuels, heating oils and heavy fuel oils.
• the heating oil or diesel fuel may be a straight atmospheric distillate, or it may contain minor amounts, e.g. up to 35 wt.%, of vacuum gas oil or cracked gas oils or of both.
• Heating oils may be made of a blend of virgin distillate, e.g. gas oil, naphtha, etc and cracked distillates, e.g. catalytic cycle shock.
• a representative specification for a diesel fuel includes a minimum flash point of 38°C and a 90% distillation point between 282 and 380°C (see ASTM Designations D-396 and D-975).
• the fuel oil may have a sulphur concentration of 0.2% by weight or less based on the weight of the fuel.
• the sulphur concentration is 0.05% by weight or less, such as 0.035% by weight or less or 0.01% by weight or less.
• the art describes methods for reducing the sulphur concentration of hydrocarbon middle distillate fuels, such methods including solvent extraction, sulfuric acid treatment, and hydrodesulphurisation.
• the additive of the invention is advantageous in the fuels having low sulphur contents, providing lubricity improvement and detergency.
• the fuel oil may be a biofuel, i.e. come from an animal or vegetable source, for example a vegetable or animal oil or both or derivatives thereof, or a mineral oil as described above in combination with biofuel.
• Vegetable oils are mainly triglycerides of monocarboxylic acids, e.g. acids containing 10-25 carbon atoms and listed below where R is an aliphatic radical of 10-25 carbon atoms which may be saturated or unsaturated.
• oils contain glycerides of a number of acids, the number and kind varying with the source vegetable of the oil.
• oils examples include rapeseed oil, tall oil, coriander oil, soyabean oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, maize oil, almond oil, palm kernel oil, coconut oil, mustard seed oil, beef tallow and fish oils.
• Rapeseed oil which is a mixture of fatty acids esterified with glycerol, is preferred as it is available in large quantities and can be obtained in a simple way by pressing from rapeseed.
• alkyl esters such as methyl esters, of fatty acids of the vegetable or animal oils. Such esters can be made by transesterification.
• the preferred alkyl esters of fatty acids are the methyl esters of oleic acid, linoleic acid, linolenic acid and erucic acid.
• the invention is particularly useful for the formulation of turbine combustion fuel oils which are generally those hydrocarbon fuels having boiling ranges within the limits of about 150° to 600°F and are designated by such terms as JP-4, JP-5, JP-7, JP-8, Jet A, Jet A-1.
• JP-4 and JP-5 are fuels defined by U.S. military specification MIL-T-5624-N and JP-8 is defined by U.S. Military Specification MIL-T83133-D. Jet A, Jet A-1 and Jet B are defined by ASTM specification D1655.
• PMA-1 Mn ⁇ 25,000 polymer (vs. polystyrene) of methacrylates of C8-C14 alcohols copolymerized with a methacrylamide of 3-(N,N-dimethylamino)propylamine.
• PMA is used in all examples as a 41.6% active ingredient solution in mineral oil, 200 ppm solution added.
• T3514 a commercial hydrocarbon soluble copolymer of an alkylvinyl monomer and a cationic vinyl monomer sold as "T3514" by Baker Petrolite as a conductivity improver.
• Fuels B and C were similarly tested with Stadis 450 and T3514. No synergistic effect was noted for Fuel B which has an inherent conductivity of 16 pS/m.
• Fuel B Fuel C Additive Treat Rate ppm Conductivity (pS/m) Conductivity (pS/m) Base Fuel 0 16 2.3
• Stadis 450 0.25 31.7 65.7 T3514 0.25 57 61.7 PMA-1 50 60.3 20.3 PMA-1+Stadis 450 50+0.25 86 266 PMA-1+T3514 50+0.25 87 115.5

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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)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Solid Fuels And Fuel-Associated Substances (AREA)

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• 2004
  • 2004-06-10 EP EP20040076708 patent/EP1502938B1/de not_active Expired - Lifetime

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