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
  • 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, 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
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
• • 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
  • C10L1/22—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, 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
  • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
  • C10L1/2462—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds
  • C10L1/2475—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon to carbon bonds

Definitions

• This invention relates to fuel oils which exhibit improved conductivity properties, to novel additive systems for providing such properties and to the use of such additives for improving the conductivity of fuel oils.
• 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.
• U.S. Patent 5,792,730 discloses the use of dispersants prepared from heavy polyamines as additives for lubricants and fuels.
• the present invention is based upon the discovery that the use in combination of an oil soluble succinimide dispersant comprising a functionalized hydrocarbon reacted with an alkylene polyamine or with a heavy alkylene polyamine 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 (65 to 315°C) 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 MILT83133-D. Jet A, Jet A-1 and Jet B are defined by ASTM specification D1655.
• an improved fuel oil composition comprising a fuel oil having an inherent conductivity of less than 15 pS/m and a two component additive system; wherein the two component additive system comprises the combination of:
• the oil soluble succinimide dispersant (a) may be represented by the formula : HRN(alkylene-NR)nH wherein n has an average value between 1 and about 11, and in one embodiment about 2 to about 7, the "alkylene” group has from 1 to about 10 carbon atoms, and in one embodiment about 2 to about 6 carbon atoms, and each R is independently hydrogen, an aliphatic or hydroxy-substituted aliphatic group of up to about 30 carbon atoms.
• alkylene polyamines include methylene polyamines, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, etc.
• polyamines include ethylene diamine, diethylene triamine, triethylene tetramine, propylene diamine, trimethylene diamine, tripropylene tetramine, tetraethylene pentamine, hexaethylene heptamine, pentaethylene hexamine, or a mixture of two or more thereof.
• Ethylene polyamines such as tetraethylene pentamine and pentaethylene hexamine are preferred.
• Suitable alkylene polyamines also include those termed "heavy polyamines" as defined hereinbelow.
• the weight ratio of the olefin polysulfone to the polymeric polyamine in component (b) is preferably in the range of 40:1 to 1:40.
• the heavy polyamine as the term is used herein includes higher oligomers or mixtures of higher oligomers of polyalkylene, e.g. polyethylene, amines containing, e.g., essentially no tetraethylenepentamine, at most small amounts of pentaethylenehexamine, but primarily oligomers with 6 to 12, preferably 7 to 12, nitrogens per molecule, with 2 or more primary amines per molecule, and more branching than conventional polyamine or polyamine mixtures.
• the heavy polyamine comprises more than 28 wt.% (e.g. > 32 wt.%) total nitrogen and an equivalent weight of primary amine groups of 120-160 grams per equivalent.
• TEPA tetraethylenepentamine
• PAM pentaethylene hexamine
• This mixture typically consists of less than 1.0 wt.% low molecular weight amine, 10-15 wt.% TEPA, 40-50 wt.% PEHA and the balance hexaethyleneheptamine (HEHA) and higher oligomers.
• PAM has 8.7-8.9 milliequivalents of primary amine per gram (an equivalent weight of 115 to 112 grams per equivalent of primary amine) and a total nitrogen content of about 33-34 wt.%.
• the oil soluble dispersant additive used in the present invention is prepared by a derivatization (imidization), using an alkylene polyamine, of functionalized hydrocarbons or polymers wherein the polymer backbones have a number average molecular weight (Mn) of greater than 300.
• Mn number average molecular weight
• the preferred number average molecular weight depends on the properties of the particular backbone. For example, for ethylene alpha olefin copolymers the preferred molecular weight is 1500 to 5000 (e.g. 2000 - 4000). For polybutenes the preferred molecular weight is 900 to 3000.
• a typical example of functionalized polymer is polyisobutenyl succinic anhydride (PIBSA) which is a reaction product of polyisobutene and maleic anhydride.
• PIBSA polyisobutenyl succinic anhydride
• This reaction can occur via halogen-assisted functionalization (e.g. chlorination), the thermal "ene” reaction, or free radical addition using a catalyst (e.g. a peroxide).
• a catalyst e.g. a peroxide
• the functionalized backbones are subsequently derivatized with an alkylene polyamine.
• the reaction with the polyamine yields a polyisobutenyl succinimide.
• 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 or dinonyl naphthalene sulphonic 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 an 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.
• oil-soluble succinimide dispersants are used in the compositions of the present invention (on an active ingredient basis, i.e., without regard to carrier oil or solvent) in amounts ranging from 5 - 400 ppm, preferably about 10 - 160 ppm (by weight), such as about 10 - 60 ppm.
• the polysulfonic-polyamine mixture conductivity improver or the alkylvinyl monomer-cationic vinyl monomer copolymer conductivity improver may each be used in amounts from 0.10-5 ppm, preferably about 0.25-1 ppm.
• compositions of this invention may also contain a phenolic antioxidant and the amount of phenolic 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 preferred antioxidant phenolic 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 o- or p- 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 include:
• the fuel oil compositions of this invention may also contain one or more other additives commonly employed in fuels and 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, low sulfur diesel fuels and ultra low sulfur diesel fuels, automotive gas oil, heating oils, premium 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 sulfur concentration of 0.2% by weight or less based on the weight of the fuel.
• the sulfur 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 sulfur concentration of hydrocarbon middle distillate fuels, such methods including solvent extraction, sulfuric acid treatment, and hydrodesulfurisation.
• the additive of the invention is advantageous in the fuels having low sulfur 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. containing 10-25 carbon atoms of the structure shown 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 (jet fuels) which are generally those hydrocarbon fuels having boiling ranges within the limits of about 150° to 600°F (65 to 315°C) 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.
• Dispersant B a succinimide made from a polyisobutenyl (Mn 1000) succinic anhydride and the same heavy polyamine used to make Dispersant A, the succinimide having 4.74% nitrogen.
• Dispersant C a succinimide made from a polyisobutenyl (Mn 950) succinic anhydride reacted with a commercial PAM mixture of ethylene polyamines, the succinimide having 2.0% nitrogen.
• Dispersant D a succinimide made from a polyisobutenyl (Mn 1000) succinic anhydride reacted with tetraethylene pentamine the succinimide having 1.35% nitrogen
• Dispersant E a succinimide made from a polyisobutenyl (Mn 2250) succinic anhydride reacted with pentaethylene hexamine the succinimide having 0.7% nitrogen
• Tet 450 66% toluene 13.3% 1-decene polysulfone, 13.3% polyamine (a reaction product of N-tallow-1,3-propylenediamine and epichlorohydrin) and 7.4% dodecylbenzene sulfonic acid.
• 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.
• Dispersants C, D and E (made with conventional ethylene polyamines, i.e., not the heavy type) were tested only in fuel 2 and showed synergy with the "Stadis 450" commercial conductivity improver. Dispersants made from the heavy polyamines show synergy with both types of commercial conductivity improvers.

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• 2005
  • 2005-02-22 EP EP05251006A patent/EP1568756A1/de not_active Withdrawn

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