EP2393905B1 - Améliorations dans les carburants. - Google Patents

Améliorations dans les carburants. Download PDF

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Publication number
EP2393905B1
EP2393905B1 EP10702900.1A EP10702900A EP2393905B1 EP 2393905 B1 EP2393905 B1 EP 2393905B1 EP 10702900 A EP10702900 A EP 10702900A EP 2393905 B1 EP2393905 B1 EP 2393905B1
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EP
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Prior art keywords
fuel
acid
compound
group
derived
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German (de)
English (en)
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EP2393905A1 (fr
Inventor
Andrea Sneddon
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Innospec Ltd
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Innospec Ltd
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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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • 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
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • 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
    • C10L1/197—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
    • 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
    • C10L1/224—Amides; Imides carboxylic acid amides, imides
    • 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
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties

Definitions

  • Bx fuels may be derived entirely from animal or vegetable oil sources (B100 fuels) or they may comprise a proportion of fuels derived from animal or vegetable oil sources, admixed with fuels from other sources (for example mineral sources, or synthetic sources, e.g. Fischer-Tropsch sources).
  • B20 herein is a fuel in which 20 wt% of the fuel is from animal or vegetable oil sources and 80 wt% of the fuel is from other sources. The proportion may be lower still, as in the case of, for example, a B5 fuel.
  • WO 2007/076163 describes such problems, and suggests that the problem of filter blocking arises as a result of the precipitation of crystals of steryl glycosides in fuels derived from biological sources. Steryl glycosides are found in plants and it is suggested that they are carried over into Bx fuels.
  • WO 2007/076163 proposed a solution to the filter blocking problem; namely the removal of the steryl glycosides, for example using an adsorbent as an additive in conjunction with a process of filtration or centrifugation, or both.
  • soy biodiesel was filtered through a bed of diatomaceous earth.
  • mineral fuels herein we mean fuels derived wholly from mineral (i.e. petroleum) sources.
  • mineral fuel component herein we mean the mineral-derived component in a Bx fuel.
  • Filter blocking problems can occur at temperatures below the cloud point in mineral and other fuels. Such problems have been closely analysed over many years. Additives have been developed that allow fuels to be used at lower temperatures than would otherwise be possible.
  • the source of the problem of precipitation below the cloud point is the presence of components such as so-called “waxes” (for example n-alkanes and methyl n-alkanoates that crystallise at low temperatures). This may cause the fuels to block filters and to become non-pourable.
  • waxes for example n-alkanes and methyl n-alkanoates that crystallise at low temperatures. This may cause the fuels to block filters and to become non-pourable.
  • Standardised tests have been devised to measure the temperature at which the fuel hazes (the cloud point - CP), the lowest temperature at which a fuel can flow (the pour point - PP) and the cold filter plugging point - CFPP); and the changes thereto caused by additives ( ⁇ CP, ⁇ PP, ⁇ CFPP).
  • the standardised tests for measuring PP and, especially, CP and CFPP are among the common working tools for persons skilled in the art. CP and CFPP may be further described as follows:
  • the cloud point of a fuel is the temperature at which a cloud of wax crystals first appears in a liquid when it is cooled under conditions prescribed in the test method as defined in ASTM D 2500.
  • US 5743923 describes the improvement of the low temperature properties of a blend of biofuel and petroleum based fuel oil by addition of an ethylene-unsaturated ester copolymer, a comb polymer, a polar N compound or a a compound having at least one linear alkyl group connected to a non-polymeric organic residue.
  • WO2007/147753 describes a paraffin dispersant for fuels, especially having a biodiesel content comprising polar oil-soluble nitrogen compounds and acid amides.
  • WO96/22344 describes chemical markers as additives in fuel oil compositions to improve filterability at temperatures above its cloud point.
  • US2008/0016754 describes additive mixtures as cold flow additives for middle distillate fuels comprising a terpolymer of ethylene, propene and at least one ethylenically unsaturated ester and a further additive selected from copolymers of ethylene and ethylenically unsaturated compounds, comb polymers and mixtures thereof.
  • CFIs cold flow improvers
  • WASAs wax anti-settling additives
  • Some such additives may assist in keeping the so-called “waxes” in solution in the mineral fuel; others may alter their crystal morphology or size, so that filterability and pourability are maintained in spite of precipitation.
  • Additives are also known which improve the CFPP of Bx grades, including B100 grade, and thus it would be expected that fuels treated in this way should have no operating problems even at temperatures significantly below the CP of the fuels.
  • the precipitate does not redissolve when the temperature is raised again. This is very different to conventional wax precipitation where at temperatures above the cloud point, wax can readily redissolve, particularly if kept dispersed in the fuel through use of WASAs.
  • a reaction product of (i) a compound containing the segment -NR 1 R 2 where R 1 represents a group containing from 4 to 44 carbon atoms and R 2 represents a hydrogen atom or a group R 1 , and (ii) carboxylic acid having from 1 to 4 carboxylic acid groups or an acid anhydride or acid halide thereof, in order to improve the filterability of a Bx fuel above the cloud point of the Bx fuel; wherein the Bx fuel comprises fuel derived from animal or vegetable oil sources admixed with fuel derived from mineral or synthetic sources; wherein the Bx fuel has a sulphur content less than 200ppm; wherein the Bx fuel contains at least 4 wt% of fuel derived from animal or vegetable sources; and wherein the additive is present in the Bx fuel in an amount (as active material) of from 10 mg/kg up to 200 mg/kg.
  • R 1 is a hydrocarbyl group or a polyethoxylate or polypropoxylate group.
  • the group R 1 is a hydrocarbyl group.
  • the group R 1 is predominantly a straight chain group.
  • hydrocarbyl denotes a group having a carbon atom directly attached to the remainder of the molecule and having a predominantly aliphatic hydrocarbon character.
  • Suitable hydrocarbyl based groups may contain non-hydrocarbon moieties. For example they may contain up to one non-hydrocarbyl group for every ten carbon atoms provided this non-hydrocarbyl group does not significantly alter the predominantly hydrocarbon character of the group.
  • groups which include for example hydroxyl, halo (especially chloro and fluoro), alkoxyl, alkyl mercapto, alkyl sulfoxy, etc.
  • the group R 1 is an-organic group entirely predominantly containing carbon and hydrogen atoms.
  • a hydrocarbyl group R 1 is preferably predominantly saturated, that is, it contain no more than one carbon-to-carbon unsaturated bond for every few (for example six to ten) carbon-to-carbon single bonds present. In the case of a hydrocarbyl group R 1 having from 4 to 10 carbon atom it may contain one unsaturated bond. In the case of a hydrocarbyl group R 1 having from 11 up to 20 carbon atom it may contain up to two unsaturated bonds. In the case of a hydrocarbyl group R 1 having from 21 up to 30 carbon atom it may contain up to three unsaturated bonds. In the case of a hydrocarbyl group R 1 having from 31 up to 40 carbon atom it may contain up to four unsaturated bonds.
  • a hydrocarbyl group R 1 having from 41 up to 44 carbon atom it may contain up to five unsaturated bonds.
  • a hydrocarbyl group R 1 is preferably a fully saturated alkyl group, preferably a fully saturated n-alkyl group.
  • a group R 1 comprises from 6 to 36 carbon atoms, prelerably 8 to 32, preferably 10 to 24, preferably 12 to 22, most preferably 14 to 20.
  • R 1 will typically include moieties with a range of carbon atoms.
  • the definitions C 4-44 ; C 14-22 are not intended to denote that all R 1 groups must fall within the stated range.
  • R 2 when present, preferably conforms to the same definitions as are given for R 1 .
  • R 1 and R 2 need not be the same.
  • R 1 and R 2 are the same.
  • the species (ii) is a carboxylic acid or an acid anhydride thereof.
  • an acid halide is used it is preferably an acid chloride.
  • Suitable compounds (i) include primary, secondary, tertiary and quaternary amines. Tertiary and quaternary amines only form amine salts.
  • Secondary amines are an especially preferred class of compounds (i).
  • especially preferred secondary amines include di-octadecylamine, di-cocoamine, di-hydrogenated tallow amine and methylbehenyl amine. Amine mixtures are also suitable such as those derived from natural materials.
  • a preferred amine is a secondary hydrogenated tallow amine, the alkyl groups of which are derived from hydrogenated tallow fat composed of approximately 3-5%wt C 14 , 30-32%wt C 16 , and 58-60%wt C 18 .
  • Quaternary amines are an especially preferred class of compounds (i).
  • R 1 and R 2 are as defined above (but R 2 is not hydrogen).
  • R 3 and R 4 independently represent a C(1-4) alkyl group, preferably propyl, ethyl or, most preferably, methyl.
  • +NR 1 R 2 (CH 3 ) 2 represents a preferred cation.
  • -An represents the anion.
  • the anion may be any suitable species but is preferably a halide, especially a chloride.
  • the reaction conditions maybe adjusted to assist the reaction between (i) and (ii).
  • the reaction conditions are adjusted by the introduction of an auxiliary base.
  • the auxiliary base is preferably an inorganic base, such as sodium methoxide, sodium ethoxide, or sodium hydroxide.
  • the inorganic base is a metal alkoxide or metal hydroxide.
  • the quaternary amine salt may be preformed as the corresponding basic salt, for example, a quaternary ammonium hydroxide or alkoxide.
  • mixtures of primary and secondary amines as species (i).
  • mixtures of secondary and quaternary amines are also preferred.
  • Preferred carboxylic acids include carboxylic acids containing two, three or four carboxylic acid groups, and acid anhydrides and acid halides thereof.
  • suitable carboxylic acids and their anhydrides induce aminoalkylenepolycarboxylic acids, for example nitrilotriacetic acid, propylene diamine tetraacetic acid, ethylenediamine tetraacetic acid, and carboxylic acids based on cyclic skeletons, e.g., pyromellitic acid, cyclohexahe-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid and naphthalene dicarboxylic acid, 1,4-dicarboxylic acids, and dialkyl spirobislactones.
  • aminoalkylenepolycarboxylic acids for example nitrilotriacetic acid, propylene diamine tetraacetic acid, ethylenediamine tetraacetic acid, and carboxylic acids based on cyclic skeletons, e.g., p
  • these acids have about 5 to 13 carbon atoms in the cyclic moiety.
  • Preferred acids useful in the present invention are optionally substituted benzene dicarboxylic acids, e.g. phthalic acid, isophthalic acid, and terephthalic acid, and their acid anhydrides or acid chlorides.
  • Optional substituents include 1-5 substituents, preferably 1-3 substituents, independently selected from C(1-4)alkyl, C(1-4)alkoxy, halogen, C(1-4)haloalkyl, C(1-4)haloalkoxy, nitrile, -COOH, -CO-OC(1-4)alkyl, and-CONR 3 R 4 where R 3 and R 4 are independently selected from hydrogen and C(1-4)alkyl.
  • Preferred halogen atoms are fluorine, chlorine and bromine However unsubstituted benzene carboxylic acids are preferred. Phthalic acid and its acid anhydride are particularly preferred.
  • the molar ratio of compound (i) to acid, acid anhydride or acid halide (ii) is such that at least 50% of the acid groups (preferably at least 75%, preferably at least 90%, and most preferably 100%) are reacted in the reaction between the compounds (i) and (ii), for example to form the amide and/or the amine salt.
  • reaction conditions may be adjusted to allow reaction between compounds (i) and (ii), for example to form the respective amide or amine salt.
  • the reaction conditions may be adjusted by raising reaction temperatures.
  • the reaction conditions may be adjusted by including a dehydrating agent within the reaction mixture.
  • the one or more carboxylic acid groups may be activated in situ ready for coupling (i) and (ii), for example, by the use of such as carbodiimides (eg. EDCl).
  • the activated forms of (ii) are preferably preformed, for example, as acid halides or acid anhydrides. Acid anhydrides are most preferred.
  • the molar ratio of compound (i) (or mixtures of compounds (i), in that situation) to acid, acid anhydride or acid halide (ii) (or mixed compounds (ii), in that situation) is at least 0.7:1, preferably 1:1, preferably at least 1.5:1.
  • it is up to 3:1, preferably up to 2.5:1.
  • Most preferably it is in the range 1.8:1 to 2.2:1.
  • a molar ratio of 2:1, (i) to (ii) is especially preferred.
  • a molar ratio of 1:1 is especially preferred.
  • compound (ii) is defined as the original starting material.
  • preferred products may be obtained by step-wise reactions involving reacting compound (i) with an adduct of compound (ii), particularly where (ii) has already reacted in with a compound (i) to form an intermediate.
  • Such an intermediate may be fully isolated or partially isolated so as to allow step-wise reactions.
  • Such an intermediate may comprise a mono-amide/mono-carboxylic acid adduct, for instance, where in a first step a first equivalent of (i) is reacted with a dicarboxylic acid, acid anhydride, or acid halide.
  • Partial isolation may therefore be mere isolation of the reaction mixture resulting from the first step of a reaction to form the mono-amide/mono-carboxylic acid.
  • a subsequent reaction of compound (i) (optionally a different compound (i) than that used in the first step) with the mono-amide/mono-carboxylic acid adduct may yield further derivatives, for instance, a diamide or a mono-amide/ammonium carboxylate salt.
  • Such a step-wise process provides for greater selectivity of either or both of an amide group and/or an ammonium salt, especially where the amines of said amide group and said ammonium group are different, such as when (i) essentially comprises more than one amine.
  • the molar ratio of-amine (i) to acid, acid anhydride or acid halide (ii) is at least 1:1, preferably at least 1.5:1. Most preferably it is in the range 1.8:1, to 2.2:1.
  • a molar ratio of 2:1, (i) to (ii) is especially preferred.
  • a quaternary ammonium salt as the only compound (i) and a dicarboxylic acid, or acid anhydride or acid halide thereof preferably the molar ratio of quaternary ammonium salt (i) to acid, acid anhydride or acid halide (ii) is at least 1:1, preferably at least 1.5:1. Most preferably it is in the range 1.8:1 to 2.2:1. A molar ratio of 2:1, (i) to (ii) is especially preferred.
  • Preferred reaction products for use in this invention contain at least the mono-amide adduct and quaternary ammonium salt and this may be achieved by using a mixture of compounds as compound (i), preferably both a secondary amine and a quaternary ammonium-compound.
  • Another preferred reaction employs both a secondary amine and a quaternary ammonium salt as compounds (i).
  • the ratio of the secondary amine to the quaternary ammonium salt in the reaction mixture is 30-70% to 70-30% molar/molar, preferably 40-60% to 60-40%, and most preferably they are present in equimolar amounts. Consistent with what is stated above, 11 therefore, this reaction employs in its most preferred embodiment equimolar amounts of the secondary amine, the quaternary ammonium salt and the acid, acid anhydride or acid halide (ii).
  • reaction between the compound (i) and the carboxylic acid, acid anhydride or acid halide forms one or more amide, imide or ammonium salts, combinations of these within the same compound, and mixtures of these compounds.
  • a dicarboxylic acid, acid anhydride or acid halide is reacted with a secondary amine in a mole ratio of 1:2 such that one mole of the amines form an amide and one mole forms an ammonium salt.
  • An especially preferred additive is a N,N-dialkylammonium salt of 2-N',N'-dialkylamide benzoic acid, which suitably is the reaction product of di(hydrogenated) tallow amine (i) and phthalic acid or its acid anhydride (ii); preferably at a molar ratio of 2:1.
  • An especially preferred additive is the reaction product of di(hydrogenated) tallow amine (i) and phthalic acid or its acid anhydride (ii); preferably at a molar ratio of 1:1.
  • reaction products hydrogenated tallow amine with EDTA reaction in a molar ratio of 4:1 with removal of four moles of water or two moles of water to form respectively the tetraamide derivative or the diamide diammonium salt derivative.
  • Another preferred additive is the reaction product of one mole of alkylspirobislactone, for example dodecenyl-spirobislactone with one mole of mono-tallow amine and one mole of di-tallow amine.
  • the fuel composition of the present invention contains at least 4 wt% of fuel derived from animal or vegetable sources, 12 preferably at least 5 wt%, at least 6 wt%, at least 8 wt%, or at least 10 wt%, of fuel derived from animal or vegetable sources. Some embodiments may contain at least 15 wt%, or at least 20 wt%, of fuel derived from animal or vegetable sources.
  • the fuel composition may contain up to 99 wt% of fuel derived from animal or vegetable sources, for example up to 95 wt%, up to 90 wt%, up to 85 wt%, up to 80 wt%, up to 75 wt%, up to 70 wt%, up to 60 wt%, up to 50 wt%, up to 40 wt%, up to 30 wt%, up to 25 wt%, up to 20 wt%, up to 15 wt%, or up to 12 wt%, of fuel derived from animal or vegetable sources.
  • up to 95 wt% up to 90 wt%, up to 85 wt%, up to 80 wt%, up to 75 wt%, up to 70 wt%, up to 60 wt%, up to 50 wt%, up to 40 wt%, up to 30 wt%, up to 25 wt%, up to 20 wt%, up to 15 wt%, or up
  • a fuel which comprises 100% fuel produced from an animal or vegetable source is denoted as B100, a fuel which comprises 90% mineral diesel and 10% biodiesel is known as B10; fuel comprising 50% mineral diesel and 50% biodiesel is known as B50; and so on.
  • Fuel of animal or vegetable origin may include ethyl or methyl esters of fatty acids of biological origin.
  • Starting materials for the production of such fuel include, but are not limited to, materials containing fatty acids. These materials include, without limitation, triacylglycerols, diacylglycerols, monoacylglycerols, phospholipids, esters, free fatty acids, or any combinations thereof.
  • the diesel is produced by incubating the material including the fatty acids with a short chain alcohol in the presence of heat, pressure, a catalyst, or combinations of any thereof to produce fatty acid esters of the short chain alcohols.
  • the fatty acids used to produce the fuel may originate from a wide variety of natural sources including, but not limited to, vegetable oil, canola oil, safflower oil, sunflower oil, nasturtium seed oil, mustard seed oil, olive oil, sesame oil, soybean oil, com oil, peanut oil, cottonseed oil, rice bran oil, babassu nut oil, castor oil, palm oil, palm oil, rapeseed oil, low erucic acid rapeseed oil, palm kernel oil, lupin oil, jatropha oil, coconut oil, flaxseed oil, evening primrose oil, jojoba oil, camelina oil, tallow, beef tallow, butter, chicken fat, lard, dairy butterfat, shea butter, used frying oil, oil miscella, used cooking oil, yellow trap grease, hydrogenated oils, derivatives of the oils, fractions of the oils, conjugated derivatives of the oils, and mixtures of any thereof. grease, hydrogenated oils, derivatives of the oils, fractions of the
  • the precipitates which form above the cloud point and which the present invention seeks to combat are not revealed by cloud point test ASTM D 2500.
  • the precipitates which form above the cloud point and which the present invention seeks to combat are not revealed immediately merely by cooling the fuel to a given temperature.
  • they form following an incubation period, by holding the fuel at a temperature above the cloud point for a incubation period.
  • the incubation period is at least 4 hours, preferably at least 12 hours, preferably at least 16 hours, preferably at least 48 hours, preferably at least 96 hours.
  • the precipitates which form above the cloud point and which the present invention seeks to combat are not removed merely by raising the temperature of the fuel above the temperature at which they formed.
  • the Bx fuel is a middle distillate fuel, generally boiling within the range of from 110 to 500, e.g. 150 to 400° C.
  • it is a Bx fuel for use in diesel engines or heating fuel oil.
  • the fuel is B100.
  • the fuel is a blend of fuel derived from animal or vegetable sources and fuel derived from mineral sources and/or synthetic sources j(e.g. FT fuels, derived from the Fischer-Tropsch process).
  • the fuel is a blend of a fuel derived from vegetable sources and a fuel derived from non-vegetable sources; preferably from mineral sources.
  • the Bx fuel may contain other flow-improving additives to provide the usual benefits, in reducing the CP and CFPP.
  • Such compounds may include CFIs and WASAs.
  • US 3048479 describes ethylene-vinyl ester pour depressants for middle distillates.
  • GB 1263152 describes distillate petroleum oil compositions containing ethylene ester copolymers. The preferred copolymers are of ethylene and vinyl acetate.
  • US 3961916 describes middle distillate compositions with improved filterability containing mixtures of two different EVA copolymers.
  • US 4211534 describes combinations of ethylene polymer, polymer having alkyl side chains, and nitrogen containing compound to improve cold flow properties of distillate fuel oils.
  • EP 153176A and EP 153177A describe polymers or copolymers containing an n-alkyl ester of a mono-ethylenically unsaturated C4 to C8 mono- or dicarboxylic acid.
  • the Bx fuel is a low sulphur content fuel, having a sulphur content less than 200 ppm, preferably less than 100 ppm, preferably less than 50 ppm, preferably less than 20 ppm, preferably less than 15 ppm, preferably less than 10 ppm.
  • the additive is present in the fuel in an amount (as active material) from 10 mg/kg fuel, preferably from 20 mg/kg fuel, preferably from 30 mg/kg fuel.
  • the additive is present in the fuel in an amount (as active material) up to 200 mg/kg fuel, preferably up to 100 mg/kg fuel, preferably up to 80 mg/kg fuel, preferably up to 60 mg/kg fuel, preferably up to 45 mg/kg fuel.
  • the additive may be added to Bx fuel which is known to exhibit a filtration problem above the cloud point, to reduce the problem or, preferably, to obviate the problem by preventing precipitation above the cloud point.
  • Reducing or solving the problem may be achieved by reducing the size or quantity of the precipitates which may appear in the Bx fuel above the cloud point, or by controlling the morphology of the precipitates in the Bx fuel above the cloud point.
  • the additive is added to Bx fuel in order to prevent the emergence of precipitates above the cloud point.
  • preventing the emergence of precipitates above the cloud point we mean that detectable precipitates do not appear in the Bx fuel under normal storage or use conditions.
  • an additive which is the reaction product of (i) a compound containing the segment -NR 1 R 2 where R 1 represents a group containing from 4 to 44 carbon atoms and R 2 represents a hydrogen atom or a group R 1 , and (ii) a carboxylic acid having from 1 to 4 carboxylic acid groups or an acid anhydride or acid halide thereof in order to prevent the emergence of precipitates in the Bx fuel above the cloud point of the Bx fuel.
  • a sample of the fuel to be tested is passed at a constant rate of flow through a glass fibre filter medium.
  • the pressure drop across the filter is monitored, and the volume of fuel passing the filter medium within a prescribed pressure drop is measured.
  • the filter blocking tendency (FBT) can be described in one of the following ways:
  • the FBT is 1.41.
  • Values of FBT >1.41 indicate that less than 300 ml pass through the filter before a pressure of 105 kPa is reached.
  • Values Of FBT ⁇ 1.41 indicate that 300ml pass through the filter at a pressure of less than 105kPa
  • the modification to the IP 387 method relates to thermal conditioning and cold soak of a sample being tested.
  • the base fuel used in these tests was a B5 fuel which met the requirements of DIN EN 590 and contained a commercially available cold flow additive believed to comprise EVA copolymers in an amount effective to achieve a CFPP of ⁇ -15°C.
  • Example Set B the testing was the same as in Example Set-A but the base fuel ("Basefuel 2") also met the requirements of DIN EN90 and was a B10 fuel prepared from a standard diesel meeting the specifications of CEC Fuel Specification RF-06-03, blended with rapeseed methyl ester (RME) and a commercially available cold flow additive believed to comprise EVA copolymers in an amount effective to achieve a CFPP of ⁇ -15oC.
  • Basefuel 2 base fuel
  • RME rapeseed methyl ester

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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)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Claims (11)

  1. Utilisation d'un produit de la réaction de (i) un composé contenant le segment -NR1R2 où R1 représente un groupe contenant de 4 à 44 atomes de carbone et R2 représente un atome d'hydrogène ou un groupe R1, et (ii) un acide carboxylique ayant de 1 à 4 groupes acide carboxylique ou un anhydride d'acide ou un halogénure d'acide de celui-ci,
    afin d'améliorer la filtrabilité d'un carburant Bx au-delà du point de trouble du carburant Bx ;
    dans laquelle le carburant Bx comprend du carburant dérivé de sources huileuses animales ou végétales mélangées avec du carburant dérivé de sources minérales ou synthétiques ;
    dans laquelle le carburant Bx a une teneur en soufre inférieure à 200 ppm ;
    dans laquelle le carburant Bx contient au moins 4 % en poids de carburant dérivé de sources animales ou végétales ;
    et dans laquelle l'additif est présent dans le carburant Bx en une quantité (sous forme de matériau actif) de 10 mg/kg jusqu'à 200 mg/kg.
  2. Utilisation selon la revendication 1, dans laquelle le groupe R1 est un groupe pratiquement saturé principalement à chaîne droite comprenant de 10 à 24 atomes de carbone.
  3. Utilisation selon la revendication 1 ou 2, dans laquelle le groupe R2 est un groupe qui se conforme aux mêmes définitions que celles indiquées à propos de R1 dans l'une quelconque des revendications précédentes.
  4. Utilisation selon la revendication 3, dans laquelle le composé (i) est une amine secondaire de formule HNR1R2 où R1 et R2 sont tels que définis dans la revendication 3 ; ou est un sel d'ammonium ayant le cation +NR1R2R3R4 où R1 et R2 sont tels que définis dans la revendication 3 et R3 et R4 représentent indépendamment un groupe alkyle en C1 à C4.
  5. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle l'acide carboxylique est choisi parmi les acides aminoalkylènepolycarboxyliques, par exemple l'acide nitrilotriacétique, l'acide propylènediamine-tétraacétique, l'acide éthylènediaminetétraacétique, les dialkylspirobislactones, et les acides carboxyliques basés sur des charpentes cycliques, ayant 5 à 13 atomes de carbone dans le fragment cyclique (et leurs anhydrides d'acide et halogénures d'acide), et dans laquelle les acides carboxyliques basés sur des charpentes cycliques sont de préférence choisis parmi l'acide pyromellitique, l'acide cyclohexane-1,2-dicarboxylique, l'acide cyclohexène-1,2-dicarboxylique, l'acide cyclopentane-1,2-dicarboxylique, l'acide naphtalènedicarboxylique, les acides 1,4-dicarboxyliques et les acides benzènedicarboxyliques.
  6. Utilisation selon la revendication 5, dans laquelle les acides benzènedicarboxyliques sont choisis parmi l'acide isophtalique, l'acide téréphtalique, et en particulier l'acide phtalique (et leurs anhydrides d'acide ou halogénures d'acide).
  7. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle le rapport molaire du composé (i) à l'anhydride d'acide ou à l'halogénure d'acide (ii) est tel qu'au moins 50 % des groupes acides (de préférence au moins 75 %, de préférence au moins 90 %, et tout spécialement 100 %) réagissent dans la réaction entre les composés (i) et (ii).
  8. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle le composé (i) est un sel d'amine secondaire et/ou d'ammonium quaternaire et le composé (ii) est un acide dicarboxylique, ou un anhydride d'acide ou halogénure d'acide de celui-ci, et dans laquelle le rapport molaire du ou des composés (i) à l'acide, l'anhydride d'acide ou l'halogénure d'acide (ii) est d'au moins 1/1, de préférence d'au moins 1,5/1, de préférence de 2/1.
  9. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle ledit additif est présent dans le carburant Bx en une quantité de 5 mg par kg de carburant à 500 mg par kg de carburant, de préférence de 10 mg par kg de carburant à 80 mg par kg de carburant, de préférence de 20 mg par kg de carburant à 60 mg par kg de carburant, de préférence de 30 mg par kg de carburant à 45 mg par kg de carburant.
  10. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle le carburant Bx est un carburant mixte comprenant un composant carburant dérivé d'une source huileuse animale ou de préférence végétale et un composant carburant dérivé d'une source minérale.
  11. Utilisation selon la revendication 10, dans laquelle le carburant Bx comprend un ou plusieurs composés qui améliorent les propriétés d'écoulement du carburant dérivé de la source minérale à une température inférieure au point de trouble du carburant Bx.
EP10702900.1A 2009-02-09 2010-02-04 Améliorations dans les carburants. Revoked EP2393905B1 (fr)

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GBGB0902009.0A GB0902009D0 (en) 2009-02-09 2009-02-09 Improvements in fuels
PCT/GB2010/050169 WO2010089594A1 (fr) 2009-02-09 2010-02-04 Améliorations de carburants

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EP2393905B1 true EP2393905B1 (fr) 2016-11-02

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0902009D0 (en) 2009-02-09 2009-03-11 Innospec Ltd Improvements in fuels
GB201201550D0 (en) * 2012-01-30 2012-03-14 Innospec Ltd Improvements in or relating to fuels
EP2778171A1 (fr) * 2013-03-15 2014-09-17 Synbias Pharma Ltd. Monohydrate cristallin d'hydrochlorure d'épirubicine
CN104371772B (zh) * 2013-08-16 2016-08-24 中国石油化工股份有限公司 一种添加剂组合物和柴油组合物及提高生物柴油氧化安定性的方法
CN104371776B (zh) * 2013-08-16 2016-08-24 中国石油化工股份有限公司 一种润滑性得到改善的低硫柴油组合物及提高低硫柴油润滑性的方法
CN104371775B (zh) * 2013-08-16 2016-05-25 中国石油化工股份有限公司 一种添加剂组合物和柴油组合物及提高生物柴油氧化安定性的方法
US9840678B2 (en) 2013-12-26 2017-12-12 Exxonmobil Research And Engineering Company Methods of inhibiting precipitation of biodiesel fuel components
WO2023233152A1 (fr) * 2022-06-01 2023-12-07 Innospec Fuel Specialties Llc Améliorations apportées à des carburants
US20240043763A1 (en) * 2022-07-26 2024-02-08 Innospec Fuel Specialties Llc Fuels
US20240059992A1 (en) * 2022-08-09 2024-02-22 Innospec Fuel Specialties Llc Fuels

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0203812A1 (fr) 1985-05-28 1986-12-03 Exxon Research And Engineering Company Composition pour l'écoulement des combustibles à base de distillats moyens
EP0413279A1 (fr) 1989-08-16 1991-02-20 Hoechst Aktiengesellschaft Utilisation de produits de réaction d'alcénylspirodilactones et d'amines comme dispersants de paraffines
WO1993004148A1 (fr) 1991-08-22 1993-03-04 Exxon Chemical Patents, Inc. Composes et compositions pour mazout
WO1993018115A1 (fr) 1992-03-03 1993-09-16 Exxon Chemical Patents Inc. Additifs pour huiles
WO1994010267A1 (fr) 1992-10-26 1994-05-11 Exxon Chemical Patents Inc. Compositions et additifs pour combustibles
WO1996022344A1 (fr) 1995-01-17 1996-07-25 Exxon Chemical Limited Compositions de mazout
WO1996023855A1 (fr) 1995-02-02 1996-08-08 Exxon Chemical Patents Inc. Compositions d'additifs de fuel oil
EP1491614A1 (fr) 2003-06-23 2004-12-29 Infineum International Limited Compositions d'huile
WO2007147753A2 (fr) 2006-06-22 2007-12-27 Basf Se Mélange constitué de composés d'azote polaires oléosolubles et d'amides d'acides en tant que dispersant de paraffine pour des carburants
EP1881054A2 (fr) 2006-07-18 2008-01-23 Clariant International Ltd. Additif destiné à l'amélioration des propriétés à froid d'huiles combustibles
EP1932899A1 (fr) 2006-12-13 2008-06-18 Infineum International Limited Améliorations de compositions de carburant
WO2010089594A1 (fr) 2009-02-09 2010-08-12 Innospec Limited Améliorations de carburants

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3048479A (en) 1959-08-03 1962-08-07 Exxon Research Engineering Co Ethylene-vinyl ester pour depressant for middle distillates
DE1914756C3 (de) 1968-04-01 1985-05-15 Exxon Research and Engineering Co., Linden, N.J. Verwendung von Ethylen-Vinylacetat- Mischpolymerisaten für Erdöl-Destillate
US3961916A (en) 1972-02-08 1976-06-08 Exxon Research And Engineering Company Middle distillate compositions with improved filterability and process therefor
US4211534A (en) * 1978-05-25 1980-07-08 Exxon Research & Engineering Co. Combination of ethylene polymer, polymer having alkyl side chains, and nitrogen containing compound to improve cold flow properties of distillate fuel oils
DE3266117D1 (en) * 1981-03-31 1985-10-17 Exxon Research Engineering Co Two-component flow improver additive for middle distillate fuel oils
EP0153177B1 (fr) 1984-02-21 1991-11-06 Exxon Research And Engineering Company Compositions de distillat moyen à caractéristiques d'écoulement à froid
JPH0649464A (ja) * 1991-04-05 1994-02-22 Lion Corp 燃料油用添加剤
RU2009174C1 (ru) * 1992-07-02 1994-03-15 Производственное объединение "Горькнефтеоргсинтез" Присадка к углеводородному топливу
DE19848621A1 (de) * 1998-10-21 2000-04-27 Basf Ag Paraffindispergatoren mit Lubricity-Wirkung für Erdölmitteldestillate
RU2155212C1 (ru) * 1999-11-10 2000-08-27 Лаврик Алексей Александрович Очищающая присадка к топливу и топливо для двигателей внутреннего сгорания
DE10155747B4 (de) * 2001-11-14 2008-09-11 Clariant Produkte (Deutschland) Gmbh Additive für schwefelarme Mineralöldestillate, umfassend einen Ester eines alkoxylierten Polyols und ein Alkylphenol-Aldehydharz
DE10357878C5 (de) * 2003-12-11 2013-07-25 Clariant Produkte (Deutschland) Gmbh Brennstofföle aus Mitteldestillaten und Ölen pflanzlichen oder tierischen Ursprungs mit verbesserten Kälteeigenschaften
US20070151146A1 (en) 2005-12-29 2007-07-05 Inmok Lee Processes of Producing Biodiesel and Biodiesel Produced Therefrom
DE102006033150B4 (de) * 2006-07-18 2008-10-16 Clariant International Limited Additive zur Verbesserung der Kälteeigenschaften von Brennstoffölen

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0203812A1 (fr) 1985-05-28 1986-12-03 Exxon Research And Engineering Company Composition pour l'écoulement des combustibles à base de distillats moyens
EP0413279A1 (fr) 1989-08-16 1991-02-20 Hoechst Aktiengesellschaft Utilisation de produits de réaction d'alcénylspirodilactones et d'amines comme dispersants de paraffines
WO1993004148A1 (fr) 1991-08-22 1993-03-04 Exxon Chemical Patents, Inc. Composes et compositions pour mazout
WO1993018115A1 (fr) 1992-03-03 1993-09-16 Exxon Chemical Patents Inc. Additifs pour huiles
WO1994010267A1 (fr) 1992-10-26 1994-05-11 Exxon Chemical Patents Inc. Compositions et additifs pour combustibles
WO1996022344A1 (fr) 1995-01-17 1996-07-25 Exxon Chemical Limited Compositions de mazout
WO1996023855A1 (fr) 1995-02-02 1996-08-08 Exxon Chemical Patents Inc. Compositions d'additifs de fuel oil
EP1491614A1 (fr) 2003-06-23 2004-12-29 Infineum International Limited Compositions d'huile
WO2007147753A2 (fr) 2006-06-22 2007-12-27 Basf Se Mélange constitué de composés d'azote polaires oléosolubles et d'amides d'acides en tant que dispersant de paraffine pour des carburants
EP1881054A2 (fr) 2006-07-18 2008-01-23 Clariant International Ltd. Additif destiné à l'amélioration des propriétés à froid d'huiles combustibles
EP1932899A1 (fr) 2006-12-13 2008-06-18 Infineum International Limited Améliorations de compositions de carburant
WO2010089594A1 (fr) 2009-02-09 2010-08-12 Innospec Limited Améliorations de carburants

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
CEN: "Automotive fuels - Diesel - Requirements and test methods", DIN EN 590:2004, March 2004 (2004-03-01), pages 1 - 15, XP055410522
CEN: "Automotive fuels - Diesel - Requirements and test methods", DIN EN 590:2009, pages 1 - 12, XP055409654, Retrieved from the Internet <URL:http://www.envirochem.hu/www.envirochem.hu/documents/EN_590_2009_hhV05.pdf>
D. SMITH: "Poor diesel fuel quality: a British Rail experience", PETROLEUM REVIEW, February 1990 (1990-02-01), pages 86 - 88, XP055409632
FILTER BLOCKING TENDENCY ('FBT
OHSHIO, N. ET AL: "Storage stability of FAME blended diesel fuels", SAE TECHNICAL PAPER 2008-01-25 05, 6 October 2008 (2008-10-06), XP055409642
T. COLEY ET AL: "New Laboratory Test for Predicting Low-temperature Operability of Diesel Fuels", JOURNAL OF THE INSTITUTE OF PETROLEUM, vol. 52, June 1966 (1966-06-01), pages 173 - 185, XP055401469

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CN102307974A (zh) 2012-01-04
KR20110116212A (ko) 2011-10-25
MX2011008351A (es) 2011-09-06
ZA201105576B (en) 2012-09-26
US20120030994A1 (en) 2012-02-09
US20180258358A1 (en) 2018-09-13
MY155651A (en) 2015-11-13
AR075382A1 (es) 2011-03-30
JP2012517494A (ja) 2012-08-02
GB0902009D0 (en) 2009-03-11
RU2011136254A (ru) 2013-03-20
KR101741851B1 (ko) 2017-05-30
BRPI1008120B1 (pt) 2018-05-15
CA2751628C (fr) 2017-06-20
AU2010212136A1 (en) 2011-09-01
CN102307974B (zh) 2015-09-02
EP2393905A1 (fr) 2011-12-14
AU2010212136B2 (en) 2014-01-16
BRPI1008120A2 (pt) 2016-03-08
US20210403821A1 (en) 2021-12-30
WO2010089594A1 (fr) 2010-08-12
RU2529426C2 (ru) 2014-09-27
SG173602A1 (en) 2011-09-29

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