EP1942175B1 - Composition d'additifs - Google Patents

Composition d'additifs Download PDF

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Publication number
EP1942175B1
EP1942175B1 EP20070119920 EP07119920A EP1942175B1 EP 1942175 B1 EP1942175 B1 EP 1942175B1 EP 20070119920 EP20070119920 EP 20070119920 EP 07119920 A EP07119920 A EP 07119920A EP 1942175 B1 EP1942175 B1 EP 1942175B1
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EP
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Prior art keywords
acid
fuel oil
fuel
reaction
composition according
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EP20070119920
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German (de)
English (en)
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EP1942175A1 (fr
Inventor
Dr. Angela Priscilla Breakspear
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Infineum International Ltd
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Infineum International Ltd
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    • 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
    • C10L1/10—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, 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1981—Condensation polymers of aldehydes or ketones
    • 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
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • 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
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/189—Carboxylic acids; metal salts thereof having at least one carboxyl group bound to an aromatic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
    • 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
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2366—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amine groups

Definitions

  • This invention relates to additive compositions, and to their use to improve the characteristics of fuel oils, especially middle distillate fuels such as diesel fuels, kerosene and jet fuel.
  • a fuel oil composition with a sulphur level below 0.05% by weight is referred to herein as a low-sulphur fuel.
  • Such low-sulphur fuels may contain an additive to enhance their lubricity.
  • additives are of several types.
  • WO 94/17160 there is disclosed a low sulphur fuel comprising a carboxylic acid ester to enhance lubricity, more especially an ester in which the acid moiety contains from 2 to 50 carbon atoms and the alcohol moiety contains one or more carbon atoms.
  • a mixture of a dimer acid, for example, the dimer of linoleic acid, and a partially esterified polyhydric alcohol is described for the same purpose.
  • U.S. Patent No. 3287273 the use of an optionally hydrogenated dimer acid glycol ester is described.
  • lubricity enhancers or anti-wear agents as they are also termed, include a sulphurized dioleyl norbornene ester (EP-A-99595 ), castor oil ( U.S. Patent No. 4375360 and EP-A-605857 ) and, in methanol-containing fuels, a variety of alcohols and acids having from 6 to 30 carbon atoms, acid and alcohol ethoxylates, mono- and di-esters, polyol esters, and olefin-carboxylic acid copolymers and vinyl alcohol polymers (also U.S. Patent No. 4375360 ).
  • EP-A-99595 sulphurized dioleyl norbornene ester
  • castor oil U.S. Patent No. 4375360 and EP-A-605857
  • methanol-containing fuels a variety of alcohols and acids having from 6 to 30 carbon atoms, acid and alcohol ethoxylates, mono- and di-esters, polyol esters, and
  • EP 0 798 364 A1 describes the use of a salt formed by the reaction between a carboxylic acid and an aliphatic amine to improve inter alia, the lubricity of a diesel fuel.
  • the amines used have hydrocarbyl groups of between 2 and 50 carbon atoms, preferably between 8 and 20 carbon atoms, with amines such as oleyl amine being exemplified.
  • US 6,277,158 describes a concentrate containing n-butlyamine oleate as a friction modifier for addition to motor gasoline.
  • US2002/0095858 relates to fuel oil compositions containing an additive formed by the reaction of a mono- or dicarboxylic acid of 6 to 50 carbon atoms with an amine having at least one branched alkyl substituent. These additives are shown to be effective lubricity enhancers for the fuel.
  • US 2002/0014034 describes the use of additives to improve the lubricity of a fuel oil.
  • a suitable additive may be formed by the reaction of N, N-dibutylamine with an acid mixture consisting of 70% fatty acids and 30% resin-based acids.
  • EP 1 640 438 A1 discloses the use of an additive composition to improve the conductivity of a fuel oil.
  • a further consequence of refining processes employed to reduce diesel fuel sulphur and aromatic contents is a reduction in the electrical conductivity of the fuel.
  • the insulating properties of low sulphur fuels represent a potential hazard to refiners, distributors and customers due to the potential for static charge accumulation and discharge.
  • Static charges can occur during pumping and especially filtration of the fuel, the release of this charge accumulation as a spark constituting a significant risk in highly flammable environments.
  • Such risks are minimised during fuel processing and handling through appropriate earthing of fuel lines and tanks combined with the use of anti-static additives.
  • These anti-static additives do not prevent the accumulation of static charges but enhance their release to the earthed fuel lines and vessels thereby controlling the risk of sparking. A number of such additives are in common usage and are available commercially.
  • EP 1 328 609 describes combinations of either a hydrocarbyl monoamine or an N-hydrocarbyl-substituted poly(alkyleneamine) with either a fatty acid containing 8 to 24 carbon atoms or an ester thereof with an alcohol or polyol of up to 8 carbon atoms.
  • the present invention is based on the observation of a negative interaction between certain lubricity improving additives and certain conductivity improving additives, and the discovery of combinations of species where this negative interaction is minimised.
  • the present invention provides an additive composition comprising a lubricity enhancer and a conductivity-improving additive; wherein the lubricity enhancer comprises a salt formed by the reaction of a carboxylic acid with di-n-butylamine; and wherein the conductivity improving additive comprises the combination of:
  • the combination of the lubricity enhancer and the conductivity-improving additive according to the present invention is able to provide both good lubricity and good conductivity to a fuel oil composition. This is in contrast to combinations of the lubricity enhancer with other conductivity-improving additives where a significant loss in conductivity performance has been observed.
  • the use of the term 'salt' to describe the product formed by the reaction of the carboxylic acid and the amine should not be taken to mean that the reaction necessarily forms a pure salt. It is presently believed that the reaction does form a salt and thus that the reaction product contains such as salt however, due to the complexity of the reaction, it is likely that other species will also be present.
  • the term 'salt' should thus be taken to include not only the pure salt species, but also the mixture of species formed during the reaction of the carboxylic acid and the amine.
  • each R' is independently a hydrocarbon group of between 2 and 45 carbon atoms, and x is an integer between 1 and 4, are suitable.
  • R' is a hydrocarbon group of 8 to 24 carbon atoms, more preferably, 12 to 20 carbon atoms.
  • x is 1 or 2, more preferably, x is 1.
  • y is 1, in which case the acid has a single R' group.
  • the acid may be a dimer, trimer or higher oligomer acid, in which case y will be greater than 1 for example 2, 3 or 4 or more.
  • R' is suitably an alkyl or alkenyl group which may be linear or branched.
  • carboxylic acids which may be used in the present invention include: lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, neodecanoic acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, caproleic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, coconut oil fatty acid, soy bean fatty acid, tall oil fatty acid, sunflower oil fatty acid, fish oil fatty acid, rapeseed oil fatty acid, tallow oil fatty acid and palm oil fatty acid.
  • the carboxylic acid comprises tall oil fatty acid (TOFA). It has been found that TOFA with a saturate content of less than 5% by weight is especially suitable. As is known in the art, TOFA contains small but variable amounts of rosin acids and isomers thereof. Preferably, TOFA with an abietic acid content of less than 5% by weight, for example, less than 2% by weight, is used.
  • TOFA tall oil fatty acid
  • the carboxylic acid comprises rapeseed oil fatty acid.
  • the carboxylic acid comprises soy bean fatty acid.
  • the carboxylic acid comprises sunflower oil fatty acid.
  • aromatic carboxylic acids and their alkyl derivatives as well as aromatic hydroxy acids and their alkyl derivatives.
  • Illustrative examples include benzoic acid, salicylic acid and acids derived from such species.
  • the carboxylic acid has an iodine value of at least 80g/100g, more preferably at least 100 g/100g, for example, at least 130 g/100g or at least 150 g/100g.
  • the salt may conveniently be produced by mixing the carboxylic acid with the amine.
  • the order in which one component is added to the other is not important.
  • the molar ratio of the amount of acid to the amount of amine is suitably from 10:1 to 1:10, preferably from 10:1 to 1:2, more preferably from 2:1 to 1:2, for example, around 1:l. In an embodiment, a molar ratio of 1.1:1 to 1:1.1 has been found to be suitable.
  • the reaction may be conducted at room temperature, but is preferably heated gently, for example to 40°C.
  • Component (a) is a condensate species derived from an alkyl ester of p-hydroxybenzoic acid.
  • H ydroxy B enzoate- F ormaldehyde C ondensates are the subject of the present Applicant's co-pending application EP 1 640 438 A and are referred to herein as HBFC.
  • the at least one ester of p-hydroxybenzoic acid comprises; (i) a straight or branched chain C 1 - C 7 alkyl ester of p-hydroxybenzoic acid; (ii) a branched chain C 8 - C 16 alkyl ester of p-hydroxybenzoic acid, or; (iii) a mixture of long chain C 8 - C 18 alkyl esters of p-hydroxybenzoic acid, at least one of said alkyls being branched.
  • the alkyl in (i) is ethyl or n-butyl.
  • the branched alkyl group in (ii) is 2-ethylhexyl or isodecyl.
  • the molar ratio of the branched ester to the other ester is in the range of 5:1 to 1:5.
  • Condensates of mixed esters may be used, for example mixed ester condensates of n-octyl and 2-ethylhexyl esters of p-hydroxybenzoic acid may be prepared.
  • the ratio of the esters in the mixed condensates may be varied as required.
  • a mixed ester condensate where the molar ratio of 2-ethylhexyl ester to n-octyl ester is 3:1 has been found to be useful.
  • Mixed ester condensates of more than two ester monomers may also be prepared.
  • the number average molecular weight of the polymeric condensation products is suitably in the range of 500 to 5000, preferably 1000 to 3000, more preferably 1000 to 2000 Mn.
  • comonomers may be added to the reaction mixture of aldehyde and alkyl ester or mixture of alkyl esters.
  • the comonomers are aromatic compounds that are sufficiently reactive to take part in the condensation reaction.
  • alkylated, arylated and acylated benzenes such as toluene, xylene, mesitylene, biphenyls and acetophenone.
  • Other comonomers include hydroxy aromatic compounds such as p-hydroxybenzoic acid, acid derivatives of p-hydroxyaromatic acids such as amides and salts, other hydroxyaromatic acids, alkylphenols, naphthols, phenylphenols, acetamidophenols, alkoxyphenols and o-alkylated, o-arylated and o-acylated phenols.
  • the hydroxy compounds should be either di- or mono- functional with regard to the condensation reaction.
  • hydroxy compounds that are di-functional should be substituted in the para- position whilst those that are mono-functional can be substituted in any position, e.g. 2,4-di-t-butylphenol - these will only incorporate at the end of a polymer chain.
  • HBFC may be prepared by the reaction between one or more aldehydes or ketones or reactive equivalents with esters of p-hydroxybenzoic acid.
  • reactive equivalent means a material that generates an aldehyde under the conditions of the condensation reaction or a material that undergoes the required condensation reaction to produce moieties equivalent to those produced by an aldehyde.
  • Typical reactive equivalents include oligomers or polymers of the aldehyde, acetals or aldehyde solutions.
  • the aldehyde may be a mono- or di- aldehyde and may contain other functional groups, such as -COOH, and these could be capable of post-reactions in the product.
  • the aldehyde or ketone or reactive equivalent preferably contains 1-8 carbon atoms, particularly preferred are formaldehyde, acetaldehyde, propionaldehyde and butyraldehyde, most preferred is formaldehyde.
  • Formaldehyde could be in the form of paraformaldehyde, trioxan or formalin.
  • HBFC may be prepared by reacting 1 molecular equivalent (M.E.) of the esters of p-hydroxybenzoic acid with about 0.5-2 M.E. of the aldehyde, preferably 0.7-1.3 M.E. and more preferably 0.8-1.2 M.E. of the aldehyde.
  • the reaction is preferably conducted in the presence of a basic or acidic catalyst, more preferably an acidic catalyst, such as p-toluenesulphonic acid.
  • the reaction is conveniently conducted in an inert solvent, such as Exxsol D60 (a non-aromatic, hydrocarbon solvent, having a boiling point of ⁇ 200°C), the water produced in the reaction being removed by azeotropic distillation.
  • the reaction is typically run at a temperature of 90-200°C, preferably 100-160°C, and may be run under reduced pressure.
  • the HBFC can be prepared in a 2-step process whereby the esters of p-hydroxybenzoic acid are first prepared in the same reaction vessel that is used for the subsequent condensation reaction.
  • the ester is prepared from the appropriate alcohol and p-hydroxybenzoic acid in an inert solvent using an acid catalyst such as p-toluenesulphonic acid, continuously removing water produced in the reaction.
  • Formaldehyde is then added and the condensation reaction conducted as described above to give the desired HBFC.
  • the solvent is a hydrocarbon solvent, such as an aromatic hydrocarbon solvent.
  • hydrocarbon solvents include petroleum fractions such as naphtha, kerosene, diesel and heater oil; aromatic hydrocarbons such as aromatic fractions, e.g. those sold under the ⁇ SOLVESSO' tradename; alcohols and/or esters; and paraffinic hydrocarbons such as hexane and pentane and isoparaffins.
  • the additive concentrate may also contain further additives as required.
  • Such further additives include, for example the following: detergents, antioxidants (to avoid fuel degradation), corrosion inhibitors, dehazers, demulsifiers, metal deactivators, antifoaming agents, cetane improvers, co-solvents, package compatibilisers, reodourants, additives to improve the regeneration of particulate traps, middle distillate cold flow improvers and other lubricity additives.
  • copolymers, terpolymers and polymers of acrylic acid or methacrylic acid or a derivative thereof may be branched or linear.
  • Suitable copolymers, terpolymers or polymers of acrylic acid or methacrylic acid or derivatives thereof are those polymers of ethylenically unsaturated monomers such as methacrylic or acrylic 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, isodecylmethacrylate, 2-ethylhexylmethacrylate and the like.
  • copolymers, terpolymers and polymers may have number average molecular weights (Mn) of 1,000 to 10,000,000 and preferably the molecular weight range is from about 5,000 to 1,000,000, most preferably 5,000 to 100,000.
  • Mn number average molecular weights
  • a mixture of copolymers, terpolymers and polymers of acrylic acid or methacrylic acid may also be used.
  • the acrylate or methacrylate monomer or derivative thereof is copolymerized with a nitrogen-containing, amine-containing or amide-containing monomer, or includes nitrogen-containing, amine-containing or amide-containing branches.
  • a nitrogen-containing, amine-containing or amide-containing monomer or includes nitrogen-containing, amine-containing or amide-containing branches.
  • This may be achieved by providing the polymer with sites suitable for grafting, and then nitrogen-containing, amine-containing or amide-containing branches, either monomers or macromonomers, are grafted onto the main chain. Transesterification reactions or amidation reactions may also be employed to produce the same products.
  • the copolymer, terpolymer or polymer will contain 0.01 to 5 wt.% nitrogen, more preferably 0.02 to 1 wt.% nitrogen, even more preferably 0.04 to 0.15 wt.% nitrogen.
  • amine-containing monomers include: the basic amino substituted olefins such as p-(2-diethylaminoethyl) styrene; basic nitrogen-containing heterocycles having a polymerizable ethylenically unsaturated substituent, such as the vinyl pyridines or the vinyl pyrrolidones; esters of amino alcohols with unsaturated carboxylic acids such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, tertiary butylaminoethyl methacrylate or dimethylaminopropyl methacrylate; amides of diamines with unsaturated carboxylic acids, such as dimethylaminopropyl methacrylamide; amides of polyamines with unsaturated carboxylic acids, examples of such polyamines being ethylene diamine (EDA), diethylene triamine (DETA), triethylene tetramine (TETA), tetraethylene
  • a copolymer of a methacrylate ester of a C 8 -C 14 alcohol with a methacrylate ester of an N,N-dialkylaminoalkyl alcohol, such as N,N dimethyl-2-aminoethanol is particularly preferred.
  • the present invention provides a fuel oil composition comprising a major proportion of a fuel oil and a minor proportion of an additive composition according to the first aspect.
  • the fuel oil composition has a conductivity which is at least 50%, preferably at least 60% of the conductivity of an equivalent fuel oil composition containing the same quantity of the conductivity-improving additive, in the absence of the lubricity enhancer.
  • the only difference between the fuel composition of the invention and the 'equivalent' fuel oil composition is the absence of the lubricity enhancer.
  • the percentage of conductivity retained is to be determined using identical measurement conditions, e.g. temperature, measuring apparatus, sample age etc.
  • the fuel oil is e.g., a petroleum-based fuel oil, especially a middle distillate fuel oil.
  • distillate fuel oils generally boil within the range of from 110°C to 500°C, e.g. 150°C to 400°C.
  • the fuel oil may comprise atmospheric distillate or vacuum distillate, cracked gas oil, or a blend in any proportion of straight run and thermally and/or refinery streams such as catalytically cracked and hydro-cracked distillates.
  • the most common petroleum distillate fuels are kerosene, jet fuels, diesel fuels, heating oils and heavy fuel oils.
  • the heating oil 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 oil or of both.
  • Fischer-Tropsch fuels also known as FT fuels
  • FT fuels include those described as gas-to-liquid (GTL) fuels, biomass-to-liquid (BTL) fuels and coal conversion fuels.
  • GTL gas-to-liquid
  • BTL biomass-to-liquid
  • coal conversion fuels coal conversion fuels.
  • syngas (CO + H 2 ) is first generated and then converted to normal paraffins by a Fischer-Tropsch process.
  • the normal paraffins may then be modified by processes such as catalytic cracking/reforming or isomerisation, hydrocracking and hydroisomerisation to yield a variety of hydrocarbons such as iso-paraffins, cyclo-paraffins and aromatic compounds.
  • the resulting FT fuel can be used as such or in combination with other fuel components and fuel types such as those mentioned in this specification.
  • fuels derived from plant or animal sources such as FAME. These may be used alone or in combination with other types of fuel.
  • the fuel oil has a sulphur content of at most 0.05% by weight, more preferably of at most 0.035% by weight, especially of at most 0.015%.
  • Fuels with even lower levels of sulphur are also suitable such as, fuels with less than 50ppm sulphur by weight, preferably less than 20 ppm, for example 10ppm or less.
  • the present invention provides the use of an additive composition according to the first aspect to improve the lubricity of a fuel oil having a sulphur content of at most 0.05% by weight, preferably at most 0.035% by weight, especially of at most 0.015%.
  • the salt is present in the fuel oil at level of between 5 and 1000ppm by weight based on the weight of the fuel oil, more preferably between 10 and 500ppm, even more preferably between 10 and 250ppm, especially between 10 and 150ppm, for example, between 50 and 150ppm.
  • the ratio of the amount of component (a) to the amount of component (b) in the additive composition is between 9:1 to 1:9, more preferably between 6:1 to 1:6, for example between 4:1 to 1:4, 3:1 to 1:3, 2:1 to 1:2 or 1:1 based on the molar amounts of active ingredient.
  • the total amount of (a) and (b) present in the fuel oil is between 0.1 and 10,000ppm of active ingredient by weight based on the weight of the fuel oil, preferably between 1 and 500ppm, more preferably between 1 and 100ppm, for example, between 3 and 50ppm.
  • FTIR analysis of the reaction product showed a reduction in the strong carboxylic acid peak at 1710cm -1 compared to the starting acid, and a corresponding appearance of carboxylate antisymmetric and symmetric stretches at 1553 and 1399 cm -1 as well as the appearance of a broad range of peaks 2300-2600cm -1 assignable to ammonium species. This was a clear indication of the formation of a salt.
  • the flash-point of the reaction product was 67°C.
  • Example 1 was repeated using a Tall oil fatty acid with a saturate content of ca. 2% and a rosin acid content of ca. 0.8%, (TOFA-2).
  • a mixture of p-hydroxybenzoic acid (1110g), isodecanol (1397g), Exxsol D60 (670g, a non-aromatic, hydrocarbon solvent, bp ⁇ 200°C), and p-toluenesulphonic acid (43g) was heated to 160°C over 1.5 hours, slowly reducing the pressure to ⁇ 200mbar.
  • the water produced in the reaction was continuously removed using a Dean and Stark apparatus. Heating was continued for a total of 4.5 hours and the vacuum released.
  • the reaction mixture was then cooled to ⁇ 80°C and then to it was added 95% paraformaldehyde (216g). The mixture was kept at 80-85°C for 2 hours and then heated to 135°C.
  • Paraformaldehyde (228g) was then added and the mixture kept at 80-85°C for 2 hours followed by an hour at 95-100°C. It was then heated to 135°C and the pressure was gradually reduced to ⁇ 120mbar. Water produced in the reaction was continuously removed using a Dean and Stark apparatus. Heating was continued for a total of 5 hours. Solvesso 150 (900g) and 2,4-di-t-butylphenol (500g) were then added to the mixture as diluents to give the final product, which had a Mn of 1150 and a Mw of 1400.
  • Fuel samples were prepared containing the conductivity-improving additives alone and containing both the conductivity-improving additives and the lubricity enhancer of Example 2 at 200ppm by weight. Results are given in Table 3 below. Each sample was tested as soon as it was prepared and again after standing for 7 and 14 days. Fuel 1 was used. The results are given as the percentage loss in measured conductivity between the sample containing only the conductivity-improving additive and the sample containing both the conductivity-improving additive and the lubricity enhancer.
  • Conductivity improving additive A1 was within the scope of the present invention being a 7:3 molar ratio of the HBFC of Example 3 and the copolymer of Example 9, where the amine content of the copolymer was 15%.
  • Conductivity improving additives C1, C2 and C3 were used for comparative purposes and were respectively;
  • Stadis ® 425 which are products of the Octel Corporation, and AS-2010 available from DBM Chemicals.

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  • 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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Combustion & Propulsion (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Claims (7)

  1. Composition d'additifs comprenant un agent augmentant le pouvoir lubrifiant et un additif améliorant la conductivité, dans laquelle l'agent augmentant le pouvoir lubrifiant comprend un sel formé par réaction d'un acide carboxylique avec la di-n-butylamine ; et dans laquelle l'additif améliorant la conductivité comprend l'association :
    (a) d'un produit polymère de condensation formé par réaction d'un aldéhyde aliphatique ou d'une cétone aliphatique, ou d'un équivalent réactif, avec au moins un ester d'acide p-hydroxybenzoïque, avec
    (b) un copolymère, terpolymère ou polymère d'acide acrylique ou d'acide méthacrylique ou d'un de ses dérivés.
  2. Composition d'additifs suivant la revendication 1, dans laquelle l'acide carboxylique comprend un acide gras ou un mélange d'acides gras, de préférence l'acide gras du tallöl, l'acide gras d'huile de colza, l'acide gras de soja ou l'acide gras d'huile de tournesol.
  3. Composition d'additifs suivant la revendication 1 ou la revendication 2, dans laquelle ledit au moins un ester d'acide p-hydroxybenzoïque comprend : (i) un ester d'alkyle en C1 à C7 à chaîne droite ou ramifiée d'acide p-hydroxybenzoïque ; (ii) un ester d'alkyle en C8 à C16 à chaîne ramifiée d'acide p-hydroxybenzoïque ; ou (iii) un mélange d'esters d'alkyle en C8 à C18 à chaîne longue d'acide p-hydroxybenzoïque, au moins un desdits groupes alkyle étant ramifié.
  4. Composition d'additifs suivant l'une quelconque des revendications précédentes, dans laquelle le copolymère, terpolymère ou polymère d'acide acrylique ou d'acide méthacrylique ou d'un de ses dérivés est copolymérisé avec un monomère contenant de l'azote, contenant une amine ou contenant un amide ; ou bien comprend des ramifications contenant de l'azote, contenant une amine ou contenant un amide.
  5. Composition de fuel-oil comprenant une proportion dominante d'un fuel-oil et une petite proportion d'une composition d'additifs suivant l'une quelconque des revendications précédentes.
  6. Composition de fuel-oil suivant la revendication 5, dans laquelle le fuel-oil comprend un fuel-oil distillé moyen ayant une teneur en soufre d'au plus 0,05 % en poids.
  7. Utilisation d'une composition d'additifs suivant l'une quelconque des revendications 1 à 4, pour améliorer le pouvoir lubrifiant d'un fuel-oil ayant une teneur en soufre d'au plus 0,05 % en poids.
EP20070119920 2006-12-13 2007-11-02 Composition d'additifs Not-in-force EP1942175B1 (fr)

Priority Applications (1)

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Application Number Priority Date Filing Date Title
EP06126043 2006-12-13
EP20070119920 EP1942175B1 (fr) 2006-12-13 2007-11-02 Composition d'additifs

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EP1942175A1 EP1942175A1 (fr) 2008-07-09
EP1942175B1 true EP1942175B1 (fr) 2012-09-26

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Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9621263D0 (en) † 1996-10-11 1996-11-27 Exxon Chemical Patents Inc Lubricity additives for fuel oil compositions

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2222362T3 (es) * 2000-03-16 2005-02-01 The Lubrizol Corporation Combustibles diesel con contenido en azufre ultra bajo con aditivo lubricante anti-estatico.
DE10058356B4 (de) * 2000-11-24 2005-12-15 Clariant Gmbh Brennstofföle mit verbesserter Schmierwirkung, enthaltend Umsetzungsprodukte aus Fettsäuren mit kurzkettigen öllöslichen Aminen
EP1640438B1 (fr) * 2004-09-17 2017-08-30 Infineum International Limited Améliorations dans les huiles combustibles.

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