EP0239320B1 - Flüssige Brennstoffzusammensetzungen - Google Patents

Flüssige Brennstoffzusammensetzungen Download PDF

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Publication number
EP0239320B1
EP0239320B1 EP87302351A EP87302351A EP0239320B1 EP 0239320 B1 EP0239320 B1 EP 0239320B1 EP 87302351 A EP87302351 A EP 87302351A EP 87302351 A EP87302351 A EP 87302351A EP 0239320 B1 EP0239320 B1 EP 0239320B1
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European Patent Office
Prior art keywords
fuel
alkanes
weight
gas oil
wax
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English (en)
French (fr)
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EP0239320A2 (de
EP0239320A3 (en
Inventor
Robert Dryden Tack
Kenneth Lewtas
Iain More
Gerald Ivan Brown
June Kathleen Costello
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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Priority claimed from GB868606656A external-priority patent/GB8606656D0/en
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Publication of EP0239320A3 publication Critical patent/EP0239320A3/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • 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
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
    • 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
    • C10L1/1691—Hydrocarbons petroleum waxes, mineral waxes; paraffines; alkylation products; Friedel-Crafts condensation products; petroleum resins; modified waxes (oxidised)
    • 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
    • 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
    • C10L1/18—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
    • 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
    • C10L1/18—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

Definitions

  • This invention relates to distillate fuel compositions containing a flow improver.
  • Heating oils and other distillate petroleum fuels e.g. diesel fuels
  • the lowest temperature at which the fuel will still flow is generally known as the pour point.
  • Effective wax crystal modification (as measured by CFPP and other operability tests, as well as simulated and field performance) can be achieved by flow improvers, mostly ethylene-vinyl acetate copolymer (EVA) based, in distillates containing up to 4 wt%-n-alkanes at 10°C below cloud point, as determined by gravimetric or DSC methods. Additive response in these distillates is normally stimulated by the refiner adjusting ASTM D-86 distillation characteristics of the distillates to increase the tail 90% to Final Boiling Point to deltas between 20°C and 25°C.
  • EVA ethylene-vinyl acetate copolymer
  • US-A-3640691 proposes that the response of the same types of middle distillate to similar additives may be improved by the addition of a paraffinic distillate fraction containing normal alkanes higher than n-hexacosane and as high as n-tetracontane to provide from 0.1 to 2 wt.% of normal alkanes of C24 and higher.
  • a paraffinic distillate fraction containing normal alkanes higher than n-hexacosane and as high as n-tetracontane to provide from 0.1 to 2 wt.% of normal alkanes of C24 and higher.
  • a paraffinic distillate fraction containing normal alkanes higher than n-hexacosane and as high as n-tetracontane to provide from 0.1 to 2 wt.% of normal alkanes of C24 and higher.
  • the most difficult to treat are those fuels obtained from high wax crudes such as those from the crudes in Australia and the Far East where the total n-alkane content of the distillate can be greater than 20%, the total content being C12 and higher n-alkanes as measured by Gas Liquid Chromatography.
  • a middle distillate responsive to flow improvers may be obtained by adjusting the total wax content of the fuel to between 5.5 and 12 wt.%, preferably by blending of high and low wax content fuels, the wax content being that precipitated with methyl ethyl ketone from 1 gram of the fuel at -20°C.
  • This technique is not a satisfactory indication of the wax content of the fuel to be treated by the additives since it is the wax precipitated between the cloud point of the fuel and its operability point which is treated by the additive and which is important to the low temperature characteristics of the fuel.
  • the ability of these fuels to respond to flow improvers is not dependent on the total wax content of the fuel.
  • a typical hard to treat distillate fuel containing 5 to 10 wt.% wax at 10°C below its cloud point and/or greater than 20 wt.% n-alkanes C12+ has the following ASTM D-86 characteristics: Initial Boiling Point 212°C 5% 234°C 10% 243°C 20% 255°C 30% 263°C 40% 279°C 50% 288°C 60% 298°C 70% 303°C 80% 321°C 90% 334°C 95% 343°C Final Boiling Point 361°C
  • a liquid fuel composition comprises a major proportion by weight of a distillate fuel containing between 4 and 10 wt.% wax at 10°C below cloud point and having a narrow n-alkane distribution, i.e. containing substantially no paraffins longer than n-triacontane (C30), a low temperature flow improver at 0.001 to 2.0 wt.% based on the weight of the distillate fuel and added n-alkanes which provide C24 and higher alkanes in a proportion greater than 0.35 wt.% of the fuel.
  • Also according to this invention is the use as a cold flow improver for a distillate fuel containing between 4 and 10 wt.% of wax at 10°C below cloud point and having a narrow carbon distribution, i.e. containing substantially no paraffins longer than n-triacontane (C30), of a mixture of a distillate fuel low temperature flow improver and added n-alkanes whose C24 and higher is greater than 0.35 wt.% of the weight of the fuel.
  • n-triacontane C30
  • the flow improvers that are employed in this invention may be any of those generally available although we prefer to use the type comprising copolymers of ethylene and at least one second unsaturated monomer.
  • the second unsaturated monomer can be another monoolefin, e.g. a C3 to C18 alpha-monoolefin or it can be an unsaturated ester, as for example, vinyl acetate, vinyl butyrate, vinyl propionate, lauryl methacrylate, ethyl acrylate or the like.
  • the second monomer can also be a mixture of an unsaturated mono or diester and a branched or straight chain alpha monoolefin.
  • copolymers can also be used, as for example mixtures of a copolymer of ethylene and vinyl acetate with an alkylated polystyrene or with an acylated polystyrene.
  • Alternative materials are the amino succinic acid derivatives, esters such as polyacrylates and esterified maleic anhydride copolymers, polyalpha olefins, etc.
  • the preferred distillate fuel flow improver useful in this invention is a copolymer consisting of 1 to 40, and preferably 1 to 20, more preferably 3 to 20 molar proportions of ethylene per molar proportion of the ethylenically unsaturated monomer, which latter monomer can be a single monomer or a mixture of such monomers in any proportion, said polymer being oil soluble and having a number average molecular weight in the range of about 1,000 to 50,000, preferably about 1,000 to about 5,000.
  • Molecular weights can be measured by cryoscopic methods or by vapor phase osmometry, for example by using a Mechrolab Vapor Phase Osmometer Model 310A.
  • the unsaturated monomers which may be homopolymerised or copolymerised with ethylene or with each other include unsaturated acids, acid anhydrides, and mono and diesters of the general formula: wherein R1 is hydrogen or methyl; R3 is a -OOCR4 or -COOR4 group wherein R4 is hydrogen or a C1 to C16, preferably C1 to C4 straight or branched chain alkyl group and R3 is hydrogen or -COOR4.
  • the monomer when R1 to R3 are hydrogen and R2 is -OOCR4,includes vinyl alcohol esters of C2 to C17 monocarboxylic acids.
  • esters examples include vinyl acetate, vinyl isobutyrate, vinyl laurate, vinyl myristate, vinyl palmitate, etc.
  • R2 is -COOR4
  • esters include C8 oxo alcohol acrylate, methyl acrylate, methyl methacrylate, lauryl acrylate, isobutyl methacrylate, palmityl alcohol ester of alpha-methacylic acid, C13 oxo alcohol esters of methacrylic acid, etc.
  • Examples of monomers wherein R1 is hydrogen and R2 and R3 are -OOCR4 groups include mono C12 oxo alcohol fumarate, di-isopropyl maleate; di-lauryl fumarate; ethyl methyl fumarate; fumaric acid, maleic acid,etc, or where R2 is H and R1 is COOR4 and R3 is CH2 COOR4 such as the itaconates.
  • Other unsaturated monomers copolymerizable with ethylene to prepare pour point depressants or flow improvers useful in this invention include C3 to C16 branched chain or straight-chain alpha monoolefins, as for example, propylene, n-octene-1, 2-ethyl decene-1, n-decene-1, etc.
  • a C2 to C16 branched or straight-chain alpha monoolefin e.g. propylene, n-octene-1, n-decene-1, etc.
  • copolymers of 3 to 40 moles of ethylene with one mole of a mixture of 30 to 99 mole percent of unsaturated ester and 70 to 1 mole percent of olefin could be used.
  • copolymers that are formed are random copolymers consisting primarily of an ethylene polymer backbone along which are distributed side chains of hydrocarbon or oxy-substituted hydrocarbon.
  • the alcohols used in preparing the esters mentioned above are isomeric mixtures of branched chain aliphatic primary alcohols prepared from olefins, such as polymers and copolymers of C3 to C4 monoolefins, reacted with carbon monoxide and hydrogen in the presence of a cobalt-containing catalyst such as cobalt carbonyl, at temperatures of about 300°F to 400°F (about 150°C to 205°C), under pressures of about 1,000 to 3,000 p.s.i. (about 70 to 210 bar) to form aldehydes.
  • the resulting aldenyde product is then hydrogenated to form the alcohol, the latter being recovered by distillation from the hydrogenated product.
  • the copolymers have a low degree of side chain branching; particularly they contain less than 10,preferably less than 8,methyl terminated side chains (other than the ester groups) per 100 methylene groups as measured by nuclear magnetic resonance, particularly 500 megahertz proton NMR analysis.
  • the flow improver is used in a concentration in the range of from about 0.001 to about 2 wt.%, preferably from about 0.005 to about 0.2 percent by weight, based on the weight of the distillate fuel being treated.
  • the second additive provides the n-alkanes greater than C24 and preferably has a carbon number distribution from about 20 to about 40.
  • the additive consist predominantly of linear alkanes although it may also contain a small amount of branched hydrocarbons.
  • the additive may be in the form of a refinery stream such as a heavy atmospheric gas oil, vacuum gas oil or heavy cracked gas oil which provides alkanes having carbon numbers in the required range. It is believed that the additive nucleates the crystallisation of the n-alkanes in the fuel and also co-crystallises with the first n-alkanes to precipitate from the fuel.
  • the preferred n-alkane distribution of the additive therefore depends upon the particular fuel. Whilst the C24 and higher n-alkane component should be greater than 0.35 wt.% based on the fuel we prefer that it be greater than 0.5 wt.%.
  • additives may also be used to give further improvements in low temperature properties, for example a diamide or preferably a half amide, half amine salt of a dicarboxylic acid or anhydride such as phthalic anhydride, and a secondary amine, the alkyl groups preferably containing 12 to 20 carbon atoms,may be added.
  • a particularly preferred compound is the half amide, half amine salt 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).
  • the amount of diamide or half amide, half amine salt which is added is usually 0.001 to 2 wt.%, preferably 0.005 to 0.2 wt.%, based on the weight of distillate fuel.
  • glycol esters such as those defined in our EP-B-0 061 895 and the esters and amines of maleic anhydride copolymers such as those defined in EP-A-0214786, and polyolefines and chlorinated polyolefines and the amines or amides of alkyl succinic anhydrides.
  • the cold flow properties of the distillate fuel can be further improved by adding thereto a wax-naphthalene condensate.
  • a typical condensate is prepared by chlorinating a wax containing n- and branched C18 to C39 paraffins (C26 average) to obtain a chlorinated wax containing about 15 weight % chlorine.
  • the chlorowax thus obtained is polymerised with naphthalene via an alkylation reaction to give a condensate containing alternating wax and naphthalene units.
  • the amount of condensate added is usually 0.00005 to 0.1 wt.% based on the weight of the distillate fuel.
  • the additives of the present invention may be supplied as concentrates for incorporation into the bulk fuel , such a concentrate comprising a solution containing from 30 to 70 wt.% ,preferably 40 to 60 wt.% ,of a mixture of copolymer of ethylene and another ethylenically unsaturated monomer and the n-alkane composition.
  • n-alkane distributions of the fuel and the vacuum gas oil were Fuel VGO C12 0.71 C13 1.08 C14 1.80 C15 2.59 C16 2.25 C18 2.53 0.40 C19 2.37 0.81 C20 2.19 1.81 C21 2.12 2.59 C22 1.70 3.74 C23 0.97 4.39 C24 0.43 4.29 C25 0.18 3.94 C26 0.08 3.24 C27 0.03 2.36 C28 0.02 1.95 C29 0.01 1.02 C30 0.003 0.73 C31 0.44 C32 0.26 C33 0.15 C34 0.14 C35 0.09 C36 0.03 C37 0.05 C38 0.02
  • the base fuel contained 23.40 wt.% of n-alkanes of C12 and higher.
  • CFPPT cold filter plugging point test
  • VGO vacuum gas oil
  • composition of the components was:
  • the base fuel contained 27.3 wt.% of alkanes C12 and higher.
  • the CFPP response to the following additives was as follows: Amount of Additive Blend 1 Blend 2 Blend 3 Additive 4 Additive 5 Additive 4 Additive 5 Additive 4 Additive 5 0 ppm -1 -1 5 5 -3 -3 500 ppm -1 -1 2 -2 -3 -3 1000 ppm -2 -2 -1 -9 -3 -3 1500 ppm -2 -2 -1 -10 -3 -3 -3
  • the base fuel contained 32 wt.% of alkanes C12 and higher.
  • This example illustrates the improvement in response to flow improvers by replacing heavy atmospheric gas oil (HGO) with heavy cracked gas oil (HCO), Base Fuel 1 had a cloud point of -1°C and use Fuel 2 of -2°C.
  • HGO heavy atmospheric gas oil
  • HCO heavy cracked gas oil
  • the Base Fuel 1 contained 22.8 wt.% n-alkanes C12 and higher and Base Fuel 2 27.6 wt.%.
  • the quantities of additive specified are the actual amounts of polymer.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (16)

  1. Flüssige Brennstoffzusammensetzung, die einen größeren Gewichtsanteil eines Destillatbrennstoffs, der bei 10°C unter dem Trübungspunkt zwischen 4 und 10 Gew.% Paraffin und im wesentlichen keine Paraffine, die länger als n-Triacontan sind, enthält, 0,001 bis 2,0 Gew.%, bezogen auf das Gewicht des Destillatbrennstoffs, eines Tieftemperatur-Fließverbesserers und zugesetzte n-Alkane umfaßt, die zugesetzte C₂₄ und höhere Alkane in einer Menge von mehr als 0,35 Gew.%, bezogen auf das Gewicht des Brennstoffs, liefern.
  2. Zusammensetzung nach Anspruch 1, bei der der Destillatbrennstoff bei 10°C unter dem Trübungspunkt etwa 8 Gew.% Paraffin enthält.
  3. Zusammensetzung nach Anspruch 1 oder 2, bei der die Menge des Fließverbesserers 0,005 bis 0,2 Gew.%, bezogen auf das Gewicht des Destillatbrennstoffs, beträgt.
  4. Zusammensetzung nach einem der vorhergehenden Ansprüche, bei der die zugesetzten n-Alkane eine Kohlenstoffzahlverteilung von 20 bis 40 besitzen.
  5. Zusammensetzung nach einem der vorhergehenden Ansprüche, bei der die dem Destillatbrennstoff zugesetzte Menge an C₂₄ und höheren n-Alkanen größer als 0,5 Gew.% des Destillatbrennstoffs ist.
  6. Zusammensetzung nach einem der vorhergehenden Ansprüche, bei der die n-Alkane zugesetzt werden, indem das Destillat mit einem Vakuumgasöl, einem schweren gecrackten Gasöl oder einem schweren atmosphärischen Gasöl vermischt wird.
  7. Zusammensetzung nach Anspruch 6, bei der 5 bis 10 Gew.% Vakuumgasöl oder schweres atmosphärisches Gasöl verwendet wird.
  8. Zusammensetzung nach Anspruch 6 oder 7, bei der Vakuumgasöl verwendet wird, das n-Alkane im wesentlichen im C₂₅- bis C₃₅-Bereich umfaßt.
  9. Zusammensetzung nach Anspruch 6 oder 7, bei der schweres atmosphärisches Gasöl verwendet wird, das n-Alkane im wesentlichen im C₁₄- bis C₃₇-Bereich umfaßt.
  10. Zusammensetzung nach einem der vorhergehenden Ansprüche, bei der der Brennstoff einen Endsiedepunkt unter 370°C besitzt.
  11. Verwendung als Kaltfließverbesserer für Destillatbrennstoff, der bei 10°C unter dem Trübungspunkt zwischen 4 und 10 Gew.% Paraffin und im wesentlichen keine Paraffine, die länger als n-Triacontan sind, enthält, von
    (a) einer Mischung aus n-Alkanen, die mindestens 0,35 Gew.%, bezogen auf das Gewicht des Brennstoffs, C₂₄ und höhere n-Alkane liefern und
    (b) 0,001 bis 2 Gew.%, bezogen auf das Gewicht des Brennstoffs, eines Tieftemperatur-Fließverbesserers.
  12. Verwendung nach Anspruch 11, die mindestens 0,5 Gew.% zugesetzte C₂₄ und höhere Alkane liefert.
  13. Verwendung nach Anspruch 11 oder 12, bei der die n-Alkane als eine Komponente in Vakuumgasöl oder schwerem Gasöl zugesetzt werden.
  14. Verwendung nach einem der Ansprüche 11 bis 13, bei der die n-Alkane 20 bis etwa 40 Kohlenstoffatome enthalten.
  15. Flüssige Brennstoffzusammensetzung, die einen größeren Gewichtsanteil eines Destillatbrennstoffs, der bei 10°C unter dem Trübungspunkt zwischen 4 und 10 Gew.% Paraffin und im wesentlichen keine Paraffine, die länger als n-Triacontan sind, enthält, 0,001 bis 2,0 Gew.%, bezogen auf das Gewicht des Destillatbrennstoffs, eines Copolymers aus Ethylen und einem ethylenisch ungesättigten Monomer und 5 bis 10 Vol.%, bezogen auf das Volumen von Destillatbrennstoff und Copolymer, eines Vakuumgasöls, schweren gecrackten Gasöls oder schweren atmosphärischen Gasöls umfaßt.
  16. Verfahren zur Verbesserung des Kaltfließverhaltens eines Destillatbrennstoffs, der bei 10°C unter dem Trübungspunkt zwischen 4 und 10 Gew.% Paraffin und im wesentlichen keine Paraffine, die länger als n-Triacontan sind, enthält, bei dem diesem 0,001 bis 2 Gew.%, bezogen auf das Gewicht des Brennstoffs, eines Tieftemperatur-Fließverbesserers und n-Alkane zugesetzt werden, die C₂₄ und höhere Alkane in einer Menge von mehr als 0,35 Gew.%, bezogen auf das Gewicht des Brennstoffs, liefern.
EP87302351A 1986-03-18 1987-03-18 Flüssige Brennstoffzusammensetzungen Expired - Lifetime EP0239320B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB868606656A GB8606656D0 (en) 1986-03-18 1986-03-18 Fuel oil compositions
GB868609293A GB8609293D0 (en) 1986-03-18 1986-04-16 Liquid fuel compositions
GB8609293 1986-04-16

Publications (3)

Publication Number Publication Date
EP0239320A2 EP0239320A2 (de) 1987-09-30
EP0239320A3 EP0239320A3 (en) 1988-01-13
EP0239320B1 true EP0239320B1 (de) 1993-12-29

Family

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Application Number Title Priority Date Filing Date
EP87302351A Expired - Lifetime EP0239320B1 (de) 1986-03-18 1987-03-18 Flüssige Brennstoffzusammensetzungen

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EP (1) EP0239320B1 (de)
JP (1) JP2514199B2 (de)
KR (1) KR950009004B1 (de)
CN (1) CN1024014C (de)
AU (1) AU590827B2 (de)
DE (1) DE3788585T2 (de)
ES (1) ES2048157T3 (de)
GB (1) GB8609293D0 (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8618397D0 (en) * 1986-07-29 1986-09-03 Exxon Chemical Patents Inc Liquid fuel compositions
JPH01103699A (ja) * 1987-07-28 1989-04-20 Sumitomo Chem Co Ltd 燃料油組成物
JPH01103698A (ja) * 1987-07-28 1989-04-20 Sumitomo Chem Co Ltd 燃料油組成物
GB9504222D0 (en) * 1995-03-02 1995-04-19 Exxon Chemical Patents Inc Fuel oil compositions
GB9725578D0 (en) 1997-12-03 1998-02-04 Exxon Chemical Patents Inc Oil additives and compositions
GB9725581D0 (en) 1997-12-03 1998-02-04 Exxon Chemical Patents Inc Additives and oil compositions
GB9725579D0 (en) 1997-12-03 1998-02-04 Exxon Chemical Patents Inc Additives and oil compositions
US6136050A (en) * 1998-06-22 2000-10-24 Tonen Corporation Diesel fuel oil composition
US7998339B2 (en) 2005-12-12 2011-08-16 Neste Oil Oyj Process for producing a hydrocarbon component
US8053614B2 (en) 2005-12-12 2011-11-08 Neste Oil Oyj Base oil
EP2078743A1 (de) 2008-01-10 2009-07-15 Shell Internationale Researchmaatschappij B.V. Kraftstoffzusammensetzung

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1264638A (de) 1968-09-17 1972-02-23
US3620696A (en) 1968-09-17 1971-11-16 Exxon Research Engineering Co Fuel oil with improved flow properties
US3640691A (en) * 1968-09-17 1972-02-08 Exxon Research Engineering Co Enhancing low-temperature flow properties of fuel oil
US3733184A (en) * 1971-02-09 1973-05-15 Exxon Co Composition for improving air-fuel ratio distribution in internal combustion engines
US4153423A (en) * 1975-03-28 1979-05-08 Exxon Research & Engineering Co. Polymer combinations useful in distillate hydrocarbon oils to improve cold flow properties
US4464182A (en) * 1981-03-31 1984-08-07 Exxon Research & Engineering Co. Glycol ester flow improver additive for distillate fuels
JPS57207696A (en) * 1981-06-17 1982-12-20 Nippon Sekiyu Seisei Kk Diesel gas oil composition
JPS6035396A (ja) * 1984-06-15 1985-02-23 Nec Corp 半導体メモリ装置の駆動方法

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KR870008998A (ko) 1987-10-22
AU7014187A (en) 1987-09-24
CN1024014C (zh) 1994-03-16
JP2514199B2 (ja) 1996-07-10
GB8609293D0 (en) 1986-05-21
DE3788585D1 (de) 1994-02-10
EP0239320A2 (de) 1987-09-30
AU590827B2 (en) 1989-11-16
JPS62270687A (ja) 1987-11-25
KR950009004B1 (ko) 1995-08-10
DE3788585T2 (de) 1994-04-28
EP0239320A3 (en) 1988-01-13
ES2048157T3 (es) 1994-03-16
CN87102962A (zh) 1987-12-16

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