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EP0360419B1 - Fuel compositions - Google Patents

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Publication number
EP0360419B1
EP0360419B1 EP89308510A EP89308510A EP0360419B1 EP 0360419 B1 EP0360419 B1 EP 0360419B1 EP 89308510 A EP89308510 A EP 89308510A EP 89308510 A EP89308510 A EP 89308510A EP 0360419 B1 EP0360419 B1 EP 0360419B1
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EP
European Patent Office
Prior art keywords
alkyl
copolymer
vinyl ether
alkyl vinyl
weight
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EP89308510A
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German (de)
English (en)
French (fr)
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EP0360419A1 (en
Inventor
Robert Dryden Tack
Rodger Frank Andrews
Marie Paterson
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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Publication of EP0360419A1 publication Critical patent/EP0360419A1/en
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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
    • C10L1/18—Organic compounds containing oxygen
    • 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
    • C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds 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 an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—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
    • C10L1/195—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
    • 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
    • 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

Definitions

  • This invention concerns fuel compositions containing a cold flow improver.
  • Mineral oils containing paraffin wax such as the distillate fuels used as diesel fuel and heating oil have the characteristic of becoming less fluid as the temperature of the oil decreases. This loss of fluidity is due to the crystallisation of the wax into plate-like crystals which eventually form a spongy mass entrapping the oil therein, the temperature at which the wax crystals begin to form being known as the Cloud Point and the temperature at which the wax prevents the oil pouring being known as the Pour Point.
  • US Patent 3,252,771 relates to the use of polymers of C16 to C18 alpha-olefins with aluminium trichloride/alkyl halide catalysts as pour depressants in distillate fuels of the "broad boiling", easy-to-treat types available in the United States in the early 1960's.
  • GB 1154966 discloses the use of certain polymers derived from mono olefinically unsaturated compounds which at least partly consist of at least one mono olefinically unsaturated aliphatic compound having an unbranched saturated hydrocarbon chain of at least 18 carbon atoms as pour point depressants for wax-containing fuels having at least 3 per cent by weight of waxes with a melting point above 35°C and a boiling point above 350°C.
  • UK Patent 1437132 suggests blends of polymers having long side chains which are particularly useful for flow improvers for petroleum fuel oils and crude oils.
  • the wax crystals which are formed do not pass through the vehicle paper fuel filters but form a permeable cake on the filter allowing the liquid fuel to pass and the wax crystals will subsequently dissolve as the engine and the fuel heats up, which can be caused by the bulk fuel being heated by recycled fuel.
  • a build up of wax can, however, block the filters, leading to diesel vehicle cold starting problems and problems during the first hour of driving in cold weather.
  • the middle distillate fuels can be for example diesel fuel, aviation fuel, kerosene or jet fuel or a heating oil or a vacuum (process) gas oil, etc.
  • suitable middle distillate fuels are those boiling in the range of 120° to 500°C (ASTM D1160), preferably those boiling in the range 150° to 400°C, for example those having a relatively high final boiling point (FBP) of above 340°C.
  • FBP final boiling point
  • the low temperature flow problem is most usually encountered with diesel fuels and with heating oils.
  • Alkyl vinyl ethers have been used alone or copolymerised with e.g. unsaturated carboxylic esters or vinyl esters as additives (e.g. viscosity index improvers and flow improvers) for crude oils and residual oils, especially those which have high wax contents, pour points around room temperature or above, and FBPs of 400°C and above (GB-A-1154966, 1274746, 1432019 and 1161188 and DE-A-2047448).
  • Such copolymers have long chain alkyl groups of 18 carbon atoms and above. They have also been used as anti-static agents for a wider variety of compositions (US-A-3677725.)
  • a fuel oil composition with improved cold flow properties comprising a major proportion by weight of a middle distillate fuel boiling in the range of 120 - 500°C and a minor proportion by weight of an additive comprising a copolymer of an alkyl vinyl ether, said copolymer being selected from:
  • the invention also includes the use as a cold flow improver in a middle distillate fuel of an alkyl vinyl ether as described above.
  • Alkyl vinyl ethers are inexpensive derivatives of alcohols and can be obtained by reaction of an alcohol with acetaldehyde followed by dehydration: or by reaction of acetylene with an alcohol catalysed by potassium (or sodium) alkoxide.
  • alkyl vinyl ethers readily polymerise under cationic conditions using an acidic catalyst, for example SnCl 2 , : BF 3 , Al 2 (SO 4 ) 3 .H 2 SO 4 .7H 2 O.
  • an acidic catalyst for example SnCl 2 , : BF 3 , Al 2 (SO 4 ) 3 .H 2 SO 4 .7H 2 O.
  • copolymers of the invention are derived from monomers having at least one relatively long chain alkyl group and at least one relatively short chain allyl group.
  • Suitable and preferred copolymers of AVE include the following:
  • Examples of these monomers include olefins, acrylate or methacrylate ester, maleic anhydride (as an intermediate) and maleate and fumarate esters.
  • AVEs copolymerise with such monomers using free-radical initiators e.g AIBN [azo-isobutyronitrile], di-t-butyl peroxide, dibutyl peroctanoate or t-butyl perbenzoate
  • free-radical initiators e.g AIBN [azo-isobutyronitrile], di-t-butyl peroxide, dibutyl peroctanoate or t-butyl perbenzoate
  • coordination - type catalysts e.g AIBN [azo-isobutyronitrile], di-t-butyl peroxide, dibutyl peroctanoate or t-butyl perbenzoate
  • These copolymers comprise:
  • a specific example is the copolymer of ethyl vinyl ether with tetradecyl, octadecyl fumarate. where n is an integer.
  • n, R 1 and R 4 are as defined above.
  • R 1 is long chain alkyl and R 4 , R 5 , R 6 and R 7 are short chain alkyl and for 4(b) R 1 is short chain alkyl and R 4 , R 5 , R 6 and R 7 are long chain alkyl.
  • Suitable examples of short chain AVEs are given in II(b) above.
  • Examples of long chain alcohols are the aliphatic alcohols, R 8 OH where R 8 is a C12 to C18 substituted or unsubstituted alkyl group.
  • Suitable examples are dodecanol, tetradecanol and octadecanol.
  • the long chain primary or secondary amine may have the formula R 9 R10HN where R 9 is hydrogen or an alkyl or aralkyl group and R10 is an alkyl or aralkyl group.
  • the alkyl groups and alkyl portions of aralkyl groups can be branched but are preferably straight chain. Suitable alkyl groups contain 12 to 18, especially 12 to 16 carbon atoms and suitable aralkyl groups contain 16 to 24 carbon atoms. Especially preferred alkyl groups are tetradecyl, hexadecyl and octadecyl or a mixture such as hexadecyl/tetradecyl.
  • polymers obtained by the copolymerisation of methyl vinyl ether with maleic anhydride followed by reaction of the copolymer with tetradecanol or with dihexadecylamine are the polymers obtained by the copolymerisation of methyl vinyl ether with maleic anhydride followed by reaction of the copolymer with tetradecanol or with dihexadecylamine.
  • the AVE copolymers should have a molecular weight of between 1,500 and 50,000, preferably between 2,500 and 15,000.
  • the AVE polymers Compared with the olefin copolymers where the methylene link is much less flexible than the ether link in the AVE polymers used in the fuel oil compositions of this invention, the AVE polymers have similar wax crystal modifier properties to for example poly-1-octadecene polymers but better oil solubility.
  • the amount of alkyl vinyl ether polymer added to the fuel oil is a minor proportion by weight and preferably this is between 0.0001 and 5.0% by weight, for example 0.001 to 0.5% by weight (active matter) based on the weight of the fuel oil.
  • the alkyl vinyl ether polymer may be conveniently dissolved in a suitable solvent to form a concentrate of from 20 to 90%, e.g. 30 to 80 weight % of polymer in the solvent.
  • suitable solvents include kerosene, aromatic naphthas, mineral lubricating oils, etc.
  • additives which may be included in the fuel oil with the alkyl vinyl ether polymer include for example other flow improvers.
  • the flow improver can be one of the following:-
  • the unsaturated comonomers from which the linear copolymers (i) are derived and which may be copolymerized with ethylene include unsaturated mono and diesters of the general formula: wherein R 2 is hydrogen or methyl; R 1 is a -OOCR 4 group or hydrocarbyl wherein R 4 is hydrogen or a C 1 to C28, more usually C 1 to C17, and preferably a C 1 to C 8 straight or branched chain alkyl groups or R 1 is a -COOR 4 group wherein R 4 is as previously described but is not hydrogen and R 3 is hydrogen or -COOR 4 as previous defined.
  • the monomer when R 1 and R 3 are hydrogen and R 2 is -OOCR 4 includes vinyl alcohol esters of C 1 to C29, more usually C 1 to C18 monocarboxylic acid, and preferably C 2 to C 5 monocarboxylic acid.
  • vinyl esters which may be copolymerized with ethylene include vinyl acetate, vinyl propionate and vinyl butyrate or isobutyrate, vinyl acetate being preferred.
  • the copolymers contain from 20 to 40 wt % of the vinyl ester more preferably from 25 to 35 wt% vinyl ester. They may also be mixtures of two copolymers such as those described in United States patent No 3961916.
  • the group R 7 is preferably C 1 to C28, more usually C 1 to C17 and more preferably a C 1 to C 8 straight or branched chain alkyl group.
  • R 5 and R 6 are preferably hydrogen and R 8 a C 1 to C20 alkyl group.
  • suitable olefins are propylene, hexene-1, octene-1, dodecene-1 and tetradecene-1.
  • the ethylene content is 50 to 65 weight per cent although higher amount can be used eg 80 weight % for ethylenepropylene copolymers.
  • these copolymers have a number average molecular weight as measured a by vapour phase osmometry of 1000 to 6000, preferably 1000 to 3000.
  • Particularly suitable linear copolymeric flow improvers (i) are copolymers of ethylene and a vinyl ester.
  • the vinyl ester can be a vinyl ester of a monocarboxylic acid, for example one containing 1 to 20 carbon atoms per molecular.
  • Examples are vinyl acetate, vinyl propionate and vinyl butyrate. Most preferred however is vinyl acetate.
  • the copolymer of ethylene and a vinyl ester will consist of 3 to 40, preferably 3 to 20, molar proportions of ethylene per molar proportion of the vinyl ester.
  • the copolymer usually has a number average molecular weight of between 1000 and 50,000, preferably between 1,500 and 5,000. The molecular weights can be measured by cryoscopic methods or by vapour phase osmometry, for example by using a Mechrolab Vapour Phase Osmometer Model 310A.
  • Particularly preferred comb copolymeric flow improvers are (ii) copolymers of an ester of fumaric acid and a vinyl ester.
  • the ester of fumaric acid can be either a mono- or a di-ester and alkyl esters are preferred.
  • the or each alkyl group can contain 6 to 30, preferably 10 to 20 carbon atoms, and mono- or di- (C14 to C18) alkyl esters are especially suitable, either as single esters or as mixed esters. Generally di-alkyl esters are preferred to mono- esters.
  • Suitable vinyl esters with which the fumarate ester is copolymerised are those described above in connection with ethylene/vinyl ester copolymers. Vinyl acetate is particularly preferred.
  • the fumarate esters are preferably copolymerised with the vinyl ester in a molar proportion of between 1.5:1 and 1:1.5, for example about 1:1.
  • These copolymers usually have a number average molecular weight of from 1000 to 100,000, as measured for example by Vapour Phase Osmometry such as by a Mechrolab Vapour Pressure Osmometer.
  • such polymers include a dialkyl fumarate/vinyl acetate copolymer eg ditetradecyl fumarate/vinyl acetate copolymer; a styrene dialkyl fumarate ester copolymer eg styrene/dihexadecyl fumarate copolymer; a poly dialkyl fumarate, eg poly (di octadecyl fumarate); an alpha-olefin dialkyl maleate copolymer eg copolymer of tetradecene and di hexadecyl maleate, a dialkyl itaconate/vinyl acetate copolymer eg dihexadecyl itaconate/vinyl acetate; poly-(n-alkyl methacrylates) eg poly(tetradecyl methacrylate); poly (n-alkyl acrylates
  • Linear polymer derived from ethylene oxide (iii) include the poly oxyalkylene esters, ethers, esters/ethers, amide/esters and mixtures thereof, particularly those containing at least one, preferably at least two C10 to C30 linear saturated alkyl groups of a polyoxyalkylene glycol group of molecular weight 100 to 5,000, preferably 200 to 5,000, the alkylene group in said polyoxyalkylene glycol containing from 1 to 4 carbon atoms.
  • European patent publication No 0,061,985 A2 describe some of these additives.
  • the preferred esters, ethers or ester/ethers may be structurally depicted by the formula: R-O-(A)-O-R 1 where R and R 1 are the same or different and may be
  • Suitable glycols generally are the substantially linear polyethylene glycol (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 10-30 carbon atoms are useful for reacting with the glycols to form the ester additives and it is preferred to use a C18-C24 fatty acid, especially behenic acids.
  • the esters may also be prepared by esterifying polyethoxylated fatty acids or polyethoxylated alcohols.
  • Examples of the monomeric compounds (iv) as flow improver include polar nitrogen containing compounds, for example an amine salt of, a mono amide or a diamide of, or a half amine salt, half amide of a dicarboxylic acid, tricarboxylic acid or anhydride thereof.
  • polar nitrogen containing compounds for example an amine salt of, a mono amide or a diamide of, or a half amine salt, half amide of a dicarboxylic acid, tricarboxylic acid or anhydride thereof.
  • These polar compounds are generally formed by reaction of at least one molar proportion of hydrocarbyl substituted amines with a molar proportion of hydrocarbyl acid having 1 to 4 carboxylic acid groups or their anhydrides; ester/amides may also be used containing 30 to 300, preferably 50 to 150 total carbon atoms.
  • These nitrogen compounds are described in US patent No 4,211, 534.
  • Suitable amines are usually long chain C12-C40 primary, secondary, tertiary or quaternary amines or mixtures thereof but shorter chain amines may be used provided the resulting nitrogen compound is oil soluble and therefore normally containing about 30 to 300 total carbon atoms.
  • the nitrogen compound preferably contains at least one straight chain C 8 -C40, preferably C14 to C24 alkyl segment.
  • the amine salt or half amine salt can be derived from a primary, secondary, tertiary or quaternary amine but the amide can only be derived from a primary or secondary amine.
  • the amines are preferably aliphatic amines and the amine is preferably a secondary amine in particular an aliphatic secondary amine of the formula R 1 R 2 NH.
  • R 1 and R 2 which can be the same or different contain at least 10 carbon atoms, especially 12 to 22 carbon atoms.
  • Examples of amines include dodecyl amine, tetradecyl amine, octadecyl amine, eicosyl amine, cocoamine, hydrogenated tallow amine and the like.
  • secondary amines examples include dioctadecyl amine, methyl-behenyl amine and the like. Amine mixtures are also suitable and many amines derived from natural materials are mixtures.
  • the preferred amine is a secondary hydrogenated tallow amine of the formula HNR 1 R 2 wherein R 1 and R 2 are alkyl groups derived from hydrogenated tallow fat composed of approximately 4% C14, 31% C16, 59% C18.
  • carboxylic acids for preparing these nitrogen compounds (and their anhydrides) include cyclo-hexane, 1,2 dicarboxylic acid, cyclohexane dicarboxylic acid, cyclopentane 1,2 dicarboxylic acid, naphthalene dicarboxylic acid, citric acid and the like. Generally, these acids will have about 3-13 carbon atoms in the cyclic moiety. Preferred acids are benzene dicarboxylic acids such as phthalic acid, terephthalic acid, and iso-phthalic acid. Phthalic acid or its anhydride is particularly preferred.
  • Suitable sulpho carboxylic acids are ortho sulpho benzoic acid and mono-alkyl sulpho succinic acid.
  • One suitable compound is the half amine salt, half amide of the dicarboxylic acid in which the amine is a secondary amine.
  • the half amine salt, half amide of phthalic acid and dihydrogenated tallow amine - Armeen 2HT (approx 4 wt% n-C14 alkyl, 30 wt% n-C16 alkyl, 60 wt% n-C18 alkyl, the remainder being unsaturated).
  • Another preferred compound is the diamide formed by dehydrating this amide-amine salt.
  • a copolymer having a number average molecular weight of about 20,000 as determined by membrane osmometry was prepared by copolymerising methyl vinyl ether and maleic anhydride using a free radical catalyst.
  • the anhydride groups of the resulting copolymer were then esterified with either n-tetradecanol, n-hexadecanol or a mixture of these two alcohols.
  • the resulting esterified copolymers are identified as C1, C2 and C3 respectively.
  • Copolymers C1, C2, C3 and C4 were added in conjunction with a prior art copolymer (X) which was an ethylene/vinyl acetate copolymer containing 36 weight % of vinyl acetate units, M n about 2,500, to three middle distillate fuel oils F1, F2 and F3 having the following ASTM D 86 distillation characteristics (all °C):
  • X ethylene/vinyl acetate copolymer containing 36 weight % of vinyl acetate units, M n about 2,500
  • middle distillate fuel oils F1, F2 and F3 having the following ASTM D 86 distillation characteristics (all °C):
  • the results of the Wax Appearance Temperature measurements are expressed in Table 1 as degrees depression below the WAT of the fuel without the additive polymers to illustrate their effectiveness as WAT (hence Cloud Point) depressants.
  • the Wax Appearance Temperature is measured by different scanning calorimetry using a Du Pont 990 differential scanning calorimeter. In the test a 10 microlitre sample of the fuel is cooled at 10°C/min from a temperature at least 30°C above the expected cloud point of the fuel. The observed onset of crystallisation is estimated, without correction for thermal lag (approximately 2°C), as the wax appearance temperature (WAT) is indicated by the differential scanning calorimeter.
  • Copolymer C4 of Example 1 was added to three further fuel oils F4, F5 and F6 having the following ASTM D86 distillation characteristics (all °C): The results of adding C4 to F4 are shown in Table 2.
  • CFPP results of adding to fuel oil F5 CFPP 0°C
  • a mixture of 1 part by weight of C4 with 4 parts by weight of a prior art copolymer mixture Y and Y alone are given.
  • Y was a 3:1 (by weight) mixture of respectively an ethylene-vinyl acetate copolymer containing about 36 wt % vinyl acetate of number average mol. wt. 2,500 and a copolymer containing about 17 wt % vinyl acetate of number average molecular weight 3000.
  • the cold flow properties of the blend were determined by the Cold Filter Plugging Point Test (CFPPT). This test is carried out by the procedure described in detail in "Journal of the Institute of Petroleum", Vol 52, No 510, June 1966 pp 173-185. In brief, a 40 ml sample of the oil to be tested is cooled by a bath maintained at about -34°C. Periodically (at each one degree Centrigrade drop in temperature starting from 10°C above the cloud point) the cooled oil is tested for its ability to flow through a fine screen within 1 minute. This cold property is tested with a device consisting of a pipette to whose lower end is attached an inverted funnel positioned below the surface of the oil to be tested.
  • CFPPT Cold Filter Plugging Point Test
  • Table 4 shows WAP, CP and WAT depressions by the C4 alone or in fuels with X added are equivalent to those with Z. Pour points with X are improved on adding C4 whereas pour point regression occurs on adding Z. This result is confirmed by slow cool tests where the sample is cooled from room temperature to -25°C in a cold box. Here Z/X 1000/100 ppm ai gave a gelled sample whereas C4/X 1000/100 ppm ai gave a completely fluid sample.

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EP89308510A 1988-08-24 1989-08-22 Fuel compositions Expired - Lifetime EP0360419B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89308510T ATE81148T1 (de) 1988-08-24 1989-08-22 Kraftstoffzusammensetzungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8820071 1988-08-24
GB888820071A GB8820071D0 (en) 1988-08-24 1988-08-24 Fuel compositions

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EP0360419A1 EP0360419A1 (en) 1990-03-28
EP0360419B1 true EP0360419B1 (en) 1992-09-30

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Application Number Title Priority Date Filing Date
EP89308510A Expired - Lifetime EP0360419B1 (en) 1988-08-24 1989-08-22 Fuel compositions

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EP (1) EP0360419B1 (no)
JP (1) JP2839291B2 (no)
KR (1) KR0134192B1 (no)
CN (1) CN1031464C (no)
AT (1) ATE81148T1 (no)
DE (1) DE68903084T2 (no)
ES (1) ES2036035T3 (no)
FI (1) FI893952A (no)
GB (1) GB8820071D0 (no)
GR (1) GR3006159T3 (no)
NO (1) NO174428C (no)
RU (1) RU1838382C (no)

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Publication number Priority date Publication date Assignee Title
US5205839A (en) * 1990-06-29 1993-04-27 Hoechst Aktiengesellschaft Terpolymers of ethylene, their preparation and their use as additives for mineral oil distillates
DE4020640A1 (de) * 1990-06-29 1992-01-02 Hoechst Ag Terpolymerisate des ethylens, ihre herstellung und ihre verwendung als additive fuer mineraloeldestillate
DE4036227A1 (de) * 1990-11-14 1992-05-21 Basf Ag Erdoelmitteldestillate mit verbesserten fliesseigenschaften in der kaelte
DE4036226A1 (de) * 1990-11-14 1992-05-21 Basf Ag Erdoelmitteldestillate mit verbesserten fliesseigenschaften in der kaelte
GB9213854D0 (en) * 1992-06-30 1992-08-12 Exxon Chemical Patents Inc Additives and fuel compositions
US5214224A (en) * 1992-07-09 1993-05-25 Comer David G Dispersing asphaltenes in hydrocarbon refinery streams with α-olefin/maleic anhydride copolymer
US5232963A (en) * 1992-07-09 1993-08-03 Nalco Chemical Company Dispersing gums in hydrocarbon streams with β-olefin/maleic anhydride copolymer
JPH07188501A (ja) * 1993-11-09 1995-07-25 Lubrizol Corp:The 曇り点降下組成物
US6846338B2 (en) 1997-07-08 2005-01-25 Clariant Gmbh Fuel oils based on middle distillates and copolymers of ethylene and unsaturated carboxylic esters
DE19729055C2 (de) * 1997-07-08 2000-07-27 Clariant Gmbh Brennstofföle auf Basis von Mitteldestillaten und Copolymeren aus Ethylen und ungesättigten Carbonsäureestern
DE10247795A1 (de) * 2002-10-14 2004-04-22 Basf Ag Verwendung von Hydrocarbylvinyletherhomopolymeren zur Verbesserung der Wirkung von Kaltfliessverbesserern
WO2024115211A1 (en) 2022-11-30 2024-06-06 Basf Se Homo- and copolymers of vinyl ethers for reducing crystallization of paraffin crystals in fuels

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NL148099B (nl) * 1966-03-17 1975-12-15 Shell Int Research Werkwijze voor het verlagen van het vloeipunt van een brandstofmengsel.
NL6709453A (no) * 1967-07-07 1969-01-09
JPS5430681B1 (no) * 1968-08-21 1979-10-02
US3677725A (en) * 1970-02-04 1972-07-18 Mobil Oil Corp Liquid hydrocarbon compositions containing antistatic agents
DE2047448A1 (de) * 1970-09-26 1972-03-30 Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen Additiv zur Viskositatserniedrigung in paraffinbasischen Rohölen
CA1006453A (en) * 1972-06-21 1977-03-08 Joseph B. Biasotti Method for transportation of waxy crude oils

Also Published As

Publication number Publication date
KR0134192B1 (ko) 1998-04-18
GB8820071D0 (en) 1988-09-28
FI893952A (fi) 1990-02-25
JP2839291B2 (ja) 1998-12-16
GR3006159T3 (no) 1993-06-21
RU1838382C (ru) 1993-08-30
KR900003343A (ko) 1990-03-26
DE68903084D1 (de) 1992-11-05
ATE81148T1 (de) 1992-10-15
NO893394D0 (no) 1989-08-23
CN1031464C (zh) 1996-04-03
CN1043157A (zh) 1990-06-20
EP0360419A1 (en) 1990-03-28
NO174428B (no) 1994-01-24
JPH02105891A (ja) 1990-04-18
DE68903084T2 (de) 1993-02-18
NO174428C (no) 1994-05-04
NO893394L (no) 1990-02-26
ES2036035T3 (es) 1993-05-01
FI893952A0 (fi) 1989-08-23

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