EP0885948B1 - Utilisation de compositions d'additifs dans un combustible - Google Patents

Utilisation de compositions d'additifs dans un combustible Download PDF

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Publication number
EP0885948B1
EP0885948B1 EP98202903A EP98202903A EP0885948B1 EP 0885948 B1 EP0885948 B1 EP 0885948B1 EP 98202903 A EP98202903 A EP 98202903A EP 98202903 A EP98202903 A EP 98202903A EP 0885948 B1 EP0885948 B1 EP 0885948B1
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EP
European Patent Office
Prior art keywords
ester
carbon atoms
fuel oil
composition
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
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EP98202903A
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German (de)
English (en)
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EP0885948A3 (fr
EP0885948A2 (fr
Inventor
Brian Davies
Allessandro Lombardi
Dhanesh Goberdhan
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Infineum USA LP
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Infineum USA LP
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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
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    • 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
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
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    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
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    • C10L1/1811—Organic compounds containing oxygen peroxides; ozonides
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    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
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    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
    • C—CHEMISTRY; METALLURGY
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    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
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    • C10L1/00—Liquid carbonaceous fuels
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    • 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
    • C10L1/1966—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 poly-carboxylic
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    • 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
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    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
    • C—CHEMISTRY; METALLURGY
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    • C10L1/00—Liquid carbonaceous fuels
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    • 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
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    • 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
    • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
    • C—CHEMISTRY; METALLURGY
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    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/224—Amides; Imides carboxylic acid amides, imides
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    • C10L1/231—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites
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    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
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Definitions

  • This invention relates to the use of additives for improving the cold flow properties of fuel oil, for example distillate petroleum fuel such as middle distillate fuel oil boiling within the range of 110°C to 500°C.
  • fuel oil for example distillate petroleum fuel such as middle distillate fuel oil boiling within the range of 110°C to 500°C.
  • wax may separate out from the fuel and impair the flow properties of the oil.
  • middle distillate fuels contain wax which precipitates at low temperatures to form large waxy crystals which tend to plug the small pore openings of fuel filters. This problem is particularly acute when the fuel is a diesel fuel because the nominal apertures in the fuel filter of diesel engines are typically of diameter between about 5 and 50 microns.
  • Additives are known in the art for overcoming the above problem and are called Flow Improvers.
  • Such additives may act as wax crystal modifiers when blended with waxy mineral oil by modifying the shape and size of crystals of the wax therein and reducing the adhesive forces between the crystals and between the wax and the oil to permit the oil to remain fluid at a lower temperature than in the absence of the additive.
  • additives are described in the art for improving the cold-flow properties of oils, for example in the form of oil-soluble addition products or condensates that may be polymeric or monomeric and as described, for example, in US-A-3,048,479; GB-A-1,263,152; US-A-3,961,961; and EP-A-0,261,957.
  • Some of the above additives have been and are used commercially as Cold Flow Improvers.
  • GB- A-1,112,808 describes ethylene-vinyl acetate copolymers in combination with rust inhibitors, anti-emulsifying agents, corrosion inhibitors, anti-oxidants, dispersants, dyes, dye-stabilisers, haze inhibitors, and anti-static additives.
  • DE-A-2 156 425 relates to middle distillate fuel oils comprising a flow-improving system containing certain pour point depressant polymers in combination with non-nitrogen-containing, oil-soluble, auxiliary, flow-improving compounds.
  • the second component of the flow-improving system may be, inter alia, an ester.
  • a first aspect of the invention is the use of a co-additive selected from component (A) which comprises an oil-soluble lubricity additive comprising an ester of a dicarboxylic acid and a polyhydroxy alcohol wherein the acid has from 2 to 50 carbon atoms, the alcohol has one or more carbon atoms and is a trihydric alcohol or a diol of the formula R 2 (OH) y wherein R 2 represents an unsubstituted polymethylene group having 1 to 10 carbon atoms and y represents an integer and is the number of hydroxy groups; and wherein the ester is composed only of carbon hydrogen and oxygen and has one or more free hydroxy groups; said use being in a composition comprising a major proportion of a fuel oil and a minor proportion of component (B) which comprises a cold flow improver additive comprising a copolymeric ethylene flow improver, and being to enhance the cold flow properties of the composition.
  • component (A) which comprises an oil-soluble lubricity additive comprising an ester of a
  • a second aspect of the invention is a process for blending additives with a fuel oil comprising
  • the fuel oil is preferably in the form of a flowing stream wherein step (i) takes places at a first station and step (ii) takes place at a second station, though the first and second stations may be co-terminous and injection be via a common injector.
  • the process can be automated so that a sensor can carry out step (iii), e.g. by measuring the cold filter plugging point (CFPP), and the information fed via a controller to control injection of one or both of components (B) and (A).
  • CFPP cold filter plugging point
  • the invention surprisingly enables less of component (B) to be used to achieve a desired cold flow improvement performance.
  • hydrocarbyl refers to a group having a carbon atom directly attached to the rest of the molecule and having a hydrocarbon or predominantly hydrocarbon character.
  • hydrocarbon groups including aliphatic (e.g. alkyl or alkenyl), alicyclic (e.g. cycloalkyl or cycloalkenyl), aromatic, and alicyclic-substituted aromatic, and aromatic-substituted aliphatic and alicyclic groups.
  • Aliphatic groups are advantageously saturated. These groups may contain non-hydrocarbon substituents provided their presence does not alter the predominantly hydrocarbon character of the group. Examples include keto, halo, hydroxy, nitro, cyano, alkoxy and acyl. If the hydrocarbyl group is substituted, a single (mono) substituent is preferred.
  • substituted hydrocarbyl groups examples include 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-ketopropyl, ethoxyethyl, and propoxypropyl.
  • the groups may also or alternatively contain atoms other than carbon in a chain or ring otherwise composed of carbon atoms. Suitable hetero atoms include, for example, nitrogen, sulphur, and, preferably, oxygen.
  • Ethylene copolymer flow improvers e.g. ethylene/unsaturated ester copolymer flow improvers have a polymethylene backbone divided into segments by oxyhydrocarbon side chains.
  • the copolymer may comprise an ethylene copolymer having, in addition to units derived from ethylene, units of the formula -CR 5 R 6 -CHR 7 - wherein R 6 represents hydrogen or a methyl group; R 5 represents a -OOCR 8 or -COOR 8 group wherein R 8 represents hydrogen or a C 1 to C 28 , preferably C 1 to C 9 , straight or branched chain alkyl group, provided that R 8 does not represent hydrogen when R 5 represents -COOR 8 ; and R 7 is hydrogen or -COOR 8 .
  • These may comprise a copolymer of ethylene with an ethylenically unsaturated ester, or derivatives thereof.
  • An example is a copolymer of ethylene with an ester of an unsaturated carboxylic acid, but the ester is preferably one of an unsaturated alcohol with a saturated carboxylic acid.
  • An ethylene-vinyl ester copolymer is advantageous; an ethylene-vinyl acetate, ethylene vinyl propionate, ethylene-vinyl hexanoate, or ethylene-vinyl octanoate copolymer is preferred.
  • the copolymers contain from 1 to 25, e.g.
  • the vinyl ester 1 to 20 mole % of the vinyl ester, more preferably from 3 to 17 mole % vinyl ester. They may also be in the form of mixtures of two copolymers such as those described in US Patent 3,961,916. Preferably, number average molecular weight, as measured by vapour phase osmometry, of the copolymer is 1,000 to 10,000, more preferably 1,000 to 5,000. If desired, the copolymers may be derived from additional comonomers, e.g. they may be terpolymers or tetrapolymers or higher polymers, for example where the additional comonomer is isobutylene or diisobutylene.
  • the copolymers may be made by direct polymerisation of comonomers. Such copolymers may also be made by transesterification, or by hydrolysis and re-esterification, of an ethylene unsaturated ester copolymer to give a different ethylene unsaturated ester copolymer.
  • ethylene vinyl hexanoate and ethylene vinyl octanoate copolymers may be made in this way, e.g. from an ethylene vinyl acetate copolymer.
  • Component (B) may be used with co-components such as one or more of the following:
  • Comb polymers are discussed in "Comb-Like Polymers. Structure and Properties", N. A. Platé and V. P. Shibaev, J. Poly. Sci. Macromolecular Revs., 8, p 117 to 253 (1974).
  • comb polymers have one or more long chain branches such as hydrocarbyl branches, such as oxyhydrocarbyl branches, having from 10 to 30 carbon atoms, pendant from a polymer backbone, said branch or branches being bonded directly or indirectly to the backbone.
  • long chain branches such as hydrocarbyl branches, such as oxyhydrocarbyl branches, having from 10 to 30 carbon atoms, pendant from a polymer backbone, said branch or branches being bonded directly or indirectly to the backbone.
  • indirect bonding include bonding via interposed atoms or groups, which bonding can include covalent and/or electrovalent bonding such as in a salt.
  • the comb polymer is a homopolymer having, or a copolymer at least 25 and preferably at least 40, more preferably at least 50, molar per cent of the units of which have, side chains containing at least 6, and preferably at least 10, atoms, selected from for example carbon, nitrogen and oxygen, in a linear chain.
  • the comb polymer may contain units derived from other monomers if desired or required. It is within the scope of the invention to include two or more different comb copolymers.
  • These comb polymers may be copolymers of maleic anhydride or fumaric acid and another ethylenically unsaturated monomer, e.g. an ⁇ -olefin or an unsaturated ester, for example, vinyl acetate. It is preferred but not essential that equimolar amounts of the comonomers be used although molar proportions in the range of 2 to 1 and 1 to 2 are suitable.
  • olefins that may be copolymerized with e.g. maleic anhydride, include 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene.
  • the copolymer may be esterified by any suitable technique and although preferred it is not essential that the maleic anhydride or fumaric acid be at least 50% esterified.
  • examples of alcohols which may be used include n-decan-1-ol, n-dodecan-1-ol, n-tetradecan-1-ol, n-hexadecan-1-ol, and n-octadecan-1-ol.
  • the alcohols may also include up to one methyl branch per chain, for example, 1-methylpentadecan-1-ol, 2-methyltridecan-1-ol.
  • the alcohol may be a mixture of normal and single methyl branched alcohols.
  • R 12 refers to the average number of carbon atoms in the alkyl group; if alcohols that contain a branch at the 1 or 2 positions are used R 12 refers to the straight chain backbone segment of the alcohol.
  • These comb polymers may especially be fumarate or itaconate polymers and copolymers such as for example those described in European Patent Applications 153 176, 153 177 and 225 688, and WO 91/16407.
  • Particularly preferred fumarate comb polymers are copolymers of alkyl fumarates and vinyl acetate, in which the alkyl groups have from 12 to 20 carbon atoms, more especially polymers in which the alkyl groups have 14 carbon atoms or in which the alkyl groups are a mixture of C 14 /C 16 alkyl groups, made, for example, by solution copolymerizing an equimolar mixture of fumaric acid and vinyl acetate and reacting the resulting copolymer with the alcohol or mixture of alcohols, which are preferably straight chain alcohols.
  • the mixture it is advantageously a 1:1 by weight mixture of normal C 14 and C 16 alcohols.
  • mixtures of the C 14 ester with the mixed C 14 /C 16 ester may advantageously be used.
  • the ratio of C 14 to C 14 /C 16 is advantageously in the range of from 1:1 to 4:1, preferably 2:1 to 7:2, and most preferably about 3:1, by weight.
  • the particularly preferred fumarate comb polymers may, for example, have a number average molecular weight in the range of 1,000 to 100,000, preferably 1,000 to 30,000, as measured by Vapour Phase Osmometry (VPO).
  • comb polymers are the polymers and copolymers of ⁇ -olefins and esterified copolymers of styrene and maleic anhydride, and esterified copolymers of styrene and fumaric acid; mixtures of two or more comb polymers may be used in accordance with the invention and, as indicated above, such use may be advantageous.
  • comb polymers are hydrocarbon polymers such as copolymers of ethylene and at least one ⁇ -olefin, preferably the ⁇ -olefin having at most 20 carbon atoms, examples being n-decene-1 and n-dodecene-1.
  • the number average molecular weight of such a copolymer is at least 30,000.
  • the hydrocarbon copolymers may be prepared by methods known in the art, for example using a Ziegler type catalyst.
  • Such compounds comprise a compound in which at least one substantially linear alkyl group having 10 to 30 carbon atoms is connected to a non-polymeric organic residue to provide at least one linear chain of atoms that includes the carbon atoms of said alkyl groups and one or more non-terminal oxygen atoms.
  • substantially linear is meant that the alkyl group is preferably straight chain, but that essentially straight chain alkyl groups having a small degree of branching such as in the form of a single methyl group may be used.
  • the compound has a least two of said alkyl groups when the linear chain may include the carbon atoms of more than one of said alkyl groups.
  • the linear chain or chains may provide part of a linking group between any two such alkyl groups in the compound.
  • the oxygen atom or atoms are preferably directly interposed between carbon atoms in the chain and may, for example, be provided in the form of a mono- or poly-oxyalkylene group, said oxyalkylene group preferably having 2 to 4 carbon atoms, examples being oxyethylene and oxypropylene.
  • chain or chains include carbon and oxygen atoms. They may also include other hetero-atoms such as nitrogen atoms.
  • the compound may be an ester where the alkyl groups are connected to the remainder of the compound as -O-CO n alkyl, or -CO-O n alkyl groups, in the former the alkyl groups being derived from an acid and the remainder of the compound being derived from a polyhydric alcohol and in the latter the alkyl groups being derived from an alcohol and the remainder of the compound being derived from a polycarboxylic acid.
  • the compound may be an ester where the alkyl groups are connected to the remainder of the compound as ⁇ O ⁇ n ⁇ alkyl groups.
  • the compound may be both an ester and an ether or it may contain different ester groups.
  • Examples include polyoxyalkylene esters, ethers, ester/ethers and mixtures thereof, particularly those containing at least one, preferably at least two, C 10 to C 30 linear alkyl groups and a polyoxyalkylene glycol group of molecular weight up to 5,000, preferably 200 to 5,000, the alkylene group in said polyoxyalkylene glycol containing from 1 to 4 carbon atoms, as described in EP-A-61 895 and in U.S. Patent No. 4,491,455.
  • esters, ethers or ester/ethers which may be used may be structurally depicted by the formula R 23 OBOR 24 where R 23 and R 24 are the same or different and may be
  • Suitable glycols generally are substantially linear polyethylene glycols (PEG) and polypropylene glycols (PPG) having a molecular weight of about 100 to 5,000, preferably about 200 to 2,000.
  • Esters are preferred and fatty acids containing from 10 to 30 carbon atoms are useful for reacting with the glycols to form the ester additives, it being preferred to use C 18 to C 24 fatty acid, especially behenic acid.
  • the esters may also be prepared by esterifying polyethoxylated fatty acids or polyethoxylated alcohols.
  • Polyoxyalkylene diesters, diethers, ether/esters and mixtures thereof are suitable as additives, diesters being preferred when the petroleum based component is a narrow boiling distillate, when minor amounts of monoethers and monoesters (which are often formed in the manufacturing process) may also be present. It is important for active performance that a major amount of the dialkyl compound is present.
  • stearic or behenic diesters of polyethylene glycol, polypropylene glycol or polyethylene/polypropylene glycol mixtures are preferred.
  • Examples of other compounds in this general category are those described in Japanese Patent Publication Nos. 2-51477 and 3-34790, and EP-A-117,108 and EP-A-326,356, and cyclic esterified ethoxylates such as described EP-A-356,256.
  • These polymers may be made directly from ethylenically unsaturated monomers or indirectly by hydrogenating the polymer made from monomers such as isoprene and butadiene.
  • Preferred hydrocarbon polymers are copolymers of ethylene and at least one ⁇ -olefin, having a number average molecular weight of at least 30,000.
  • the ⁇ -olefin has at most 20 carbon atoms.
  • Examples of such olefins are propylene, 1-butene, isobutene, n-octene-1, isooctene-1, n-decene-1, and n-dodecene-1.
  • the copolymer may also comprise small amounts, e.g. up to 10% by weight of other copolymerizable monomers, for example olefins other than ⁇ -olefins, and non-conjugated dienes.
  • the preferred copolymer is an ethylene-propylene copolymer. It is within the scope of the invention to include two or more different ethylene- ⁇ -olefin copolymers of this type.
  • the number average molecular weight of the ethylene- ⁇ -olefin copolymer is, as indicated above, at least 30,000, as measured by gel permeation chromatography (GPC) relative to polystyrene standards, advantageously at least 60,000 and preferably at least 80,000. Functionally no upper limit arises but difficulties of mixing result from increased viscosity at molecular weights above about 150,000, and preferred molecular weight ranges are from 60,000 and 80,000 to 120,000.
  • GPC gel permeation chromatography
  • the copolymer has a molar ethylene content between 50 and 85 per cent. More advantageously, the ethylene content is within the range of from 57 to 80%, and preferably it is in the range from 58 to 73%; more preferably from 62 to 71%, and most preferably 65 to 70%.
  • Preferred ethylene- ⁇ -olefin copolymers are ethylene-propylene copolymers with a molar ethylene content of from 62 to 71% and a number average molecular weight in the range 60,000 to 120,000, especially preferred copolymers are ethylene-propylene copolymers with an ethylene content of from 62 to 71% and a molecular weight from 80,000 to 100,000.
  • the copolymers may be prepared by any of the methods known in the art, for example using a Ziegler type catalyst.
  • the polymers are substantially amorphous, since highly crystalline polymers are relatively insoluble in fuel oil at low temperatures.
  • the additive composition may also comprise a further ethylene- ⁇ -olefin copolymer, advantageously with a number average molecular weight of at most 7500, advantageously from 1,000 to 6,000, and preferably from 2,000 to 5,000, as measured by vapour phase osmometry.
  • ⁇ -olefins are as given above, or styrene, with propylene again being preferred.
  • the ethylene content is from 60 to 77 molar per cent although for ethylene-propylene copolymers up to 86 molar per cent by weight ethylene may be employed with advantage.
  • hydrocarbon polymers examples are described in WO-A-9 111 488.
  • the oil-soluble polar nitrogen compound is either ionic or non-ionic and is capable of acting as a wax crystal growth inhibitor in fuels. It comprises for example one or more of the compounds (i) to (iii) as follows:
  • the fuel oil is suitably a middle distillate fuel oil.
  • distillate fuel oils generally boil within the range of about 110°C to about 500°C, e.g. 150° to about 400°C.
  • 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 fuel, diesel fuels, heating oil 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 oils or of both.
  • the fuel oil may be animal, vegetable or mineral oil and may also be synthetic. It may also contain additives other than those mentioned hereinbefore.
  • the concentration of the additive combination in the oil may for example be in the range of 1 to 5,000 ppm of additive (active ingredient) by weight per weight of fuel, such as 10 to 2000 ppm (active ingredient) by weight per weight of fuel, preferably 25 to 500 ppm, more preferably 100 to 200 ppm.
  • the additive should be soluble in the oil to the extent of at least 1000 ppm by weight of oil at ambient temperature. However, at least some of the additive may come out of solution near the cloud point of the oil in order to modify the wax crystals that form.
  • Concentrates are convenient as a means for incorporating the additive into bulk oil such as distillate fuel, which incorporation may be done by methods known in the art.
  • the concentrates may also contain other additives as required and preferably contain from 3 to 75 wt %, more preferably 3 to 60 wt %, most preferably 10 to 50 wt % of the additives preferably in solution in oil.
  • carrier liquid are organic solvents including hydrocarbon solvents, for example petroleum fractions such as naphtha, kerosene and heater oil; aromatic hydrocarbon containing aromatic fractions (e.g. Solvesso (trade name)); and paraffinic hydrocarbons such as hexane, pentane and isoparaffins, and includes mixtures of the above.
  • the carrier liquid must, of course, be selected having regard to its compatibility with the additive and with the fuel.
  • the additives of the invention may be incorporated into bulk oil by other methods such as those known in the art. If others are required, they may be incorporated into the bulk oil at the same time as the additives of the invention or at a different time.
  • additives include antioxidants, corrosion inhibitors, dehazers, metal deactivators, cosolvents, package compatibilisers, reodorants, antistatic additives (conductivity improvers), biocides, dyes, smoke reducers, catalyst life enhancers, power boosters, additives for fuel economy, demulsifiers, and spray modifiers.
  • Additives were dissolved in the fuels and the following tests performed on fuel treated with additives to measure the following in order to assess the effectiveness of the additives tested as filterability improvers in distillate fuels.
  • the test was carried out by the procedure substantially as described in EP-A-0,403,097 and is a variation of the CFPP test.
  • a sample of the oil to be tested (40 ml) is cooled in a bath which is maintained at about -34°C to give non-linear cooling at about 1°C/min.
  • the cooled oil tested for its ability to flow through a fine screen in a prescribed time period using a test device which is a pipette to whose lower end is attached an inverted funnel which is positioned below the surface of the oil to be tested. Stretched across the mouth of the funnel is a 350 mesh screen having an area defined by a 12 millimetre diameter.
  • the periodic tests are each initiated by applying a vacuum to the upper end of the pipette whereby oil is drawn through the screen up into the pipette to a mark indicating 20 ml of oil. After each successful passage, the oil is returned immediately to the CFPP tube. The test is repeated with each one degree drop in temperature until the oil fails to fill the pipette within 60 seconds, the temperature at which failure occurs being reported as the CFPP temperature.
  • ⁇ SFPP and ⁇ CFPP represent the difference between the SFPP (or CFPP) of the base fuel and that of the treated fuel •
  • the figures under the component codes are treat rates of active ingredient in parts per million per weight of fuel • * represent results for additive combination of the invention • a dash means that no readings were taken B2 A5 ⁇ CFPP ⁇ SFPP 60 3 0 100 1.5 0 0.5 1 100 3.5 0 60 40 7 3*
  • the additive combinations of the invention may also be effective in reducing the tendency of wax in the fuel to settle (i.e. they may be wax anti-settling additives) and may exhibit activity in slow cooling tests such as the Extended Programmed Cooling Test (XPCT) which is known in the art.
  • XPCT Extended Programmed Cooling Test

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Claims (30)

  1. Utilisation d'un co-additif (A) qui comprend un additif lubrifiant, soluble dans l'huile, comprenant un ester d'un acide dicarboxylique et d'un alcool polyhydroxylique, dans laquelle l'acide a 2 à 50 atomes de carbone, l'alcool a un ou plusieurs atomes de carbone et est un alcool trihydroxylique ou un diol de formule R2(OH)y dans laquelle R2 représente un groupe polyméthyle non substitué ayant 1 à 10 atomes de carbone et y représente un nombre entier et est le nombre de groupes hydroxy ; et dans laquelle l'ester est constitué seulement de carbone, d'hydrogène et d'oxygène et possède un ou plusieurs groupes hydroxy libres ; ladite utilisation étant l'utilisation dans une composition comprenant une proportion dominante de fuel-oil et une petite proportion du constituant (B) qui comprend un additif améliorant l'écoulement à froid, comprenant un agent améliorant l'écoulement à froid à base d'éthylène copolymère, destiné à améliorer les propriétés d'écoulement à froid de la composition.
  2. Utilisation suivant la revendication 1, dans laquelle l'additif lubrifiant comprend l'ester d'un acide dicarboxylique aliphatique à chaîne droite ou ramifiée, saturé ou insaturé.
  3. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle l'additif lubrifiant comprend l'ester d'un acide dicarboxylique de formule

            R'(COOH)2

    dans laquelle R' représente un groupe polyméthylène, substitué ou non substitué, ayant 2 à 50 atomes de carbone.
  4. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle l'additif lubrifiant comprend l'ester d'un alcool trihydroxylique.
  5. Utilisation suivant la revendication 4, dans laquelle l'alcool trihydroxylique est le glycérol.
  6. Utilisation suivant l'une quelconque des revendications 1 à 3, dans laquelle l'additif lubrifiant comprend l'ester d'un diol.
  7. Utilisation suivant la revendication 6, dans laquelle l'additif lubrifiant comprend l'ester obtenu en faisant réagir de l'acide dilinoléique avec de l'éthylèneglycol et en neutralisant les groupes acides avec du méthanol.
  8. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle l'additif lubrifiant comprend un ester ayant un poids moléculaire égal ou supérieur à 200.
  9. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle le constituant (B) comprend un copolymère éthylène/ester insaturé.
  10. Utilisation suivant la revendication 9, dans laquelle l'ester insaturé est un ester d'un alcool insaturé avec un acide carboxylique saturé.
  11. Utilisation suivant l'une quelconque des revendications précédentes, comprenant en outre, comme co-additif, un composé azoté polaire, soluble dans l'huile, portant un ou plusieurs substituants de formule

            -NR1-,

    dans laquelle R1 représente un groupe hydrocarbyle contenant 8 à 40 atomes de carbone, ce substituant ou bien un ou plusieurs de ces substituants étant facultativement sous forme d'un cation qui en est dérivé.
  12. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle le fuel-oil est fuel-oil distillé moyen.
  13. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle la concentration totale des constituants (A) et (B) dans le fuel-oil est comprise dans l'intervalle de 25 à 500 ppm d'ingrédient actif en poids par poids de fuel-oil.
  14. Composition de fuel-oil comprenant une proportion dominante d'un fuel-oil et une association :
    d'un constituant (A) qui comprend un additif lubrifiant, soluble dans l'huile, comprenant un ester d'un acide dicarboxylique et d'un alcool polyhydroxylique, dans laquelle l'acide a 2 à 50 atomes de carbone, l'alcool a un ou plusieurs atomes de carbone et est un alcool trihydroxylique ou diol de formule R2(OH)y dans laquelle R2 représente un groupe polyméthylène non substitué ayant 1 à 10 atomes de carbone et y représente un nombre entier et est le nombre de groupes hydroxy ; et dans lequel l'ester est constitué seulement de carbone, d'hydrogène et d'oxygène et possède un ou plusieurs groupes hydroxy libres ; et
    d'un constituant (B) qui comprend un additif améliorant l'écoulement à froid, comprenant un agent améliorant l'écoulement à base d'éthylène copolymère ; et
    facultativement, d'autres additifs.
  15. Concentré d'additifs contenant :
    un constituant (A) qui comprend un additif lubrifiant, soluble dans l'huile, comprenant un ester d'un acide dicarboxylique et d'un alcool polyhydroxylique dans lequel l'acide a 2 à 50 atomes de carbone, l'alcool a un ou plusieurs atomes de carbone et est un alcool trihydroxylique ou un diol de formule R2(OH)y dans laquelle R2 représente un groupe polyméthylène non substitué ayant 1 à 10 atomes de carbone et y représente un nombre entier et est le nombre de groupes hydroxy ; et dans lequel l'ester est constitué seulement de carbone, d'hydrogène et d'oxygène et possède un ou plusieurs groupes hydroxy libres ; et
    un constituant (B) qui comprend un additif améliorant l'écoulement à froid, comprenant un agent améliorant l'écoulement à base d'éthylène copolymère ; et
    facultativement, d'autres additifs.
  16. Composition suivant la revendication 14 ou la revendication 15, dans laquelle l'additif lubrifiant comprend l'ester d'un acide dicarboxylique aliphatique, à chaîne droite ou ramifiée, saturé ou insaturé.
  17. Composition suivant l'une quelconque des revendications 14 à 16, dans laquelle l'additif lubrifiant comprend l'ester d'un acide dicarboxylique de formule

            R'(COOH)2

    dans laquelle R' représente un groupe polyméthylène, substitué ou non substitué, ayant 2 à 50 atomes de carbone.
  18. Composition suivant l'une quelconque des revendications 14 à 17, dans laquelle l'additif lubrifiant comprend l'ester d'un alcool trihydroxylique.
  19. Composition suivant la revendication 18, dans laquelle l'alcool trihydroxylique est le glycérol.
  20. Composition suivant l'une quelconque des revendications 14 à 17, dans laquelle l'additif lubrifiant comprend l'ester d'un diol.
  21. Composition suivant la revendication 20, dans laquelle l'additif lubrifiant comprend l'ester obtenu en faisant réagir de l'acide dilinoléique avec de l'éthylèneglycol et en neutralisant les groupes acides avec du méthanol.
  22. Composition suivant l'une quelconque des revendications 14 à 21, dans laquelle l'additif lubrifiant comprend un ester ayant un poids moléculaire égal ou supérieur à 200.
  23. Composition suivant l'une quelconque des revendications 14 à 22, dans laquelle le constituant (B) comprend un copolymère éthylène/ester insaturé.
  24. Composition suivant la revendication 23, dans laquelle l'ester insaturé est un ester d'un alcool insaturé avec un acide carboxylique saturé.
  25. Composition suivant l'une quelconque des revendications 14 à 24, comprenant en outre, comme coadditif, un composé azoté polaire, soluble dans l'huile, portant un ou plusieurs substituants de formule

            -NR1-,

    dans laquelle R1 représente un groupe hydrocarbyle contenant 8 à 40 atomes de carbone, ce substituant ou bien un ou plusieurs de ces substituants étant facultativement sous forme d'un cation qui en est dérivé.
  26. Composition suivant la revendication 14, ou suivant l'une quelconque des revendications 16 à 25 lorsqu'elle dépend de la revendication 14, dans laquelle le fuel-oil est un fuel-oil distillé moyen.
  27. Composition suivant la revendication 14, ou suivant l'une quelconque des revendications 16 à 26 lorsqu'elle dépend de la revendication 14, dans laquelle la concentration totale des constituants (A) et (B) dans le fuel-oil est comprise dans l'intervalle de 25 à 500 ppm d'ingrédient actif en poids par poids de fuel-oil.
  28. Procédé pour mélanger des additifs à un fuel-oil, comprenant les étapes consistant :
    (i) à injecter le constituant (B) tel que défini dans la revendication 1 dans le fuel-oil ;
    (ii) à injecter le constituant (A) tel que défini dans la revendication 1 dans le fuel-oil ;
    (iii) à mesurer les propriétés d'écoulement à froid du fuel-oil après les injections des étapes (i) et (ii) ; et
    (iv) à ajuster les vitesses relatives d'injection des constituants (B) et (A) et ainsi leurs proportions relatives pour tenir compte des résultats de l'étape (iii) et pour obtenir les propriétés désirées d'écoulement à froid dans le fuel-oil.
  29. Procédé suivant la revendication 28, dans lequel le fuel-oil comprend un courant en écoulement de ce fuel-oil, l'étape (i) s'effectuant à un premier poste et l'étape (ii) s'effectuant à un second poste.
  30. Procédé suivant la revendication 28 ou 29, dans lequel un capteur met en oeuvre l'étape (iii) et l'information est transmise par un moyen de commande pour commander l'injection de l'un des ou des deux constituants (B) et (A).
EP98202903A 1993-07-22 1994-07-22 Utilisation de compositions d'additifs dans un combustible Revoked EP0885948B1 (fr)

Applications Claiming Priority (3)

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GB9315205 1993-07-22
GB939315205A GB9315205D0 (en) 1993-07-22 1993-07-22 Additives and fuel compositions
EP94924280A EP0721492B2 (fr) 1993-07-22 1994-07-22 Additifs et compositons de combustibles

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JP (1) JPH09503530A (fr)
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NO960254L (no) 1996-03-15
DE69434213T2 (de) 2006-01-26
DE69420736T2 (de) 2000-03-09
EP0721492A1 (fr) 1996-07-17
EP0721492B2 (fr) 2002-06-19
EP0721492B1 (fr) 1999-09-15
CA2167672A1 (fr) 1995-02-02
EP0908507A1 (fr) 1999-04-14
KR960704015A (ko) 1996-08-31
KR100325574B1 (ko) 2002-07-03
WO1995003377A1 (fr) 1995-02-02
JPH09503530A (ja) 1997-04-08
DE69420736T3 (de) 2002-11-07
DE69434213D1 (de) 2005-02-03
NO960254D0 (no) 1996-01-22
CA2167672C (fr) 2005-06-21
EP0885948A3 (fr) 1999-01-27
GB9315205D0 (en) 1993-09-08
DE69420736D1 (de) 1999-10-21
EP0885948A2 (fr) 1998-12-23
NO321605B1 (no) 2006-06-12

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