EP0968259A1 - Fuel oil compositions - Google Patents
Fuel oil compositionsInfo
- Publication number
- EP0968259A1 EP0968259A1 EP98917104A EP98917104A EP0968259A1 EP 0968259 A1 EP0968259 A1 EP 0968259A1 EP 98917104 A EP98917104 A EP 98917104A EP 98917104 A EP98917104 A EP 98917104A EP 0968259 A1 EP0968259 A1 EP 0968259A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- range
- fuel
- ppmw
- composition according
- fuel oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
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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
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
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- 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
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- 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
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- C10L1/14—Organic compounds
- C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
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- 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
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- C10L1/14—Organic compounds
- C10L1/16—Hydrocarbons
- C10L1/1608—Well defined compounds, e.g. hexane, benzene
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- 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
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- C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/1811—Organic compounds containing oxygen peroxides; ozonides
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
- C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
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- 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
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- C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
- C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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- C10L1/188—Carboxylic acids; metal salts thereof
- C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
- C10L1/1883—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom polycarboxylic acid
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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- C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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- C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
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- 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
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- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
- C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
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- 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
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- 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
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- 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
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- 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
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- C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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Definitions
- This invention relates to fuel oil compositions, processes for their preparation, and their use in compression-ignition engines.
- sulphur-containing compounds in general are regarded as providing anti-wear properties and a result of the reduction in their proportions, together with the reduction in proportions of other components providing lubricity, has been an increase in reported failures of fuel pumps in diesel engines using low-sulphur fuels, the failure being caused by wear in, for example, cam plates, rollers, spindles and drive shafts.
- This problem may be expected to become worse in future because, in order to meet stricter requirements on exhaust emissions generally, high pressure fuel pumps, for example rotary and unit injector systems, are being introduced, these being expected to have more stringent lubricity requirements than present equipment, at the same time as lower sulphur levels in fuels become more widely required.
- a typical sulphur content in a diesel fuel is about 0.25% by weight (2500 ppmw) .
- maximum sulphur levels have been reduced to 0.05% (500 ppmw) ; in Sweden grades of fuel with levels below 0.005% (50 ppmw) (Class 2) and 0.001% (10 ppmw) (Class 1) are already being introduced.
- low-sulphur fuels are those having a sulphur level below 0.05% by weight (500 ppmw) .
- R is derived from a polymer RH of an olefin containing from 2 to 5 carbon atoms, which polymer contains from 30 to 200 carbon atoms.
- the molecular weight of the radical R is said to range from 400 to 3000, more preferably, 900 to 1200 and is advantageously derived from a polymer of isobutene having a molecular weight of about 1000.
- the single example of the preparation of such a succinimide is based on polysibotuylene of molecular weight about 1000, and tests are described using the resulting succinimide in gasoline and in a high-sulphur diesel fuel (sulphur content of 0.5% w, i.e. 5,000 ppmw).
- EP-B-147 240 (Ethyl) describes a distillate fuel composition for indirect injection compression ignition engines containing in an amount sufficient to suppress and preferably to minimise coking in nozzles of indirect injection compression ignition engines operated on such fuel a combination of (a) organic nitrate ignition accelerator and (b) hydrocarbyl- substituted succinimide or succinamide, and optionally: (c) hydrocarbyl amine having from 3 to 60 carbons and from 1 to 10 nitrogens, or a combination of the hydrocarbyl amine (c) and (d) N, N ' -disalicylidene-1, 2- diaminopropane .
- the hydrocarbyl-substituted succinimide is preferably an olefin-polymer substituted succinimide wherein the olefin polymer substituent has an average molecular weight of 500-500,000, preferably being a polyisobutene substituent having an average molecular weight of 700-5,000.
- the succinimide portion is preferably derived from a polyalkyleneamine of formula H2N- (R-NH) n -H wherein R is a divalent aliphatic hydrocarbon having 2 to 4 carbon atoms and n is an integer from 1 to 10, including mixtures thereof, and the polyalkyleneamine is preferably a polyethyleneamine having 2 to 6 ethylene units.
- the most preferred succinimide-succinamide component is the commercial product "HITEC E -644" (trade mark), which is used in the examples and is described as being "made by reacting two moles of a polyisobutenyl succinic anhydride with one mole of a polyethylene amine mixture having an average composition corresponding to tetraethylene pentamine" (Page 7, lines 4 to 6) .
- the base fuel used in the examples was a high-sulphur fuel (sulphur content of 0.41%w, i.e. 4,100 ppmw).
- EP-A-482 253 (Ethyl) describes a fuel composition which comprises a liquid middle distillate hydrocarbonaceous fuel containing at least one fuel- soluble ashless dispersant in an amount of at least 50 ppm sufficient to cause a prompt reduction in emissions released upon combustion of said fuel composition.
- the ashless dispersant is described as "a polyisobutenyl succinimide of tetraethylene pentamine in which the number average molecular weight of the polyisobutenyl group is about 950; used as a 75% solution in high aromatic solvent” (Page 10, lines 11 to 13), and the base fuel was a high-sulphur fuel (sulphur content of 0.125%w (Page 10, line 27), i.e.
- EP-A-613 938 describes hydrocarbon fuel compositions comprising a hydrocarbon fuel and a hydrocarbyl succinic diamide derived from a secondary amine.
- the hydrocarbon fuel may suitably comprise a hydrocarbon fraction boiling in the gasoline range or a hydrocarbon fraction boiling in the diesel range” (Page 5 lines 10 and 11) . There is no discussion of sulphur content.
- the engine tests in the examples are in an Open Kadett engine (clearly a spark-ignition engine) and as comparative examples there are used (1) a mono- succinimide derived from a polyisobutylene succinic anhydride of PIB Mn about 1000 and tetraethylene pentamine and (2) a bis-succinimide derived from the same polyisobutylene succinic anhydride and triethylene tetramine.
- the mono-succinimide gave results which were significantly inferior to the bis-succinimide (deposits mg/valve of 229 compared with 40; valve rating of 8.0 compared with 9.70) (Page 9, Table 2).
- EP-B-557 561 discloses fuel compositions comprising a major amount of hydrocarbons boiling in the gasoline or diesel range and an effective detergent amount of an additive composition comprising: (a) a polyisobutenyl succinimide having the formula
- R is a polyisobutenyl group having a number average molecular weight in the range of 1200 to 1500, preferably 1200 to 1400, more preferably 1250 to 1350, and most preferably about 1300, and x is 1 or 2; and (b) a nonvolatile paraffinic or naphthenic carrier oil, or a mixture thereof.
- the deposit control tests in the examples are in gasoline, and as comparative examples there are described monosuccinimides (PIB Mn 950) of ethylenediamine (Example 1) and of diethylenetriamine (Example 2) . These are shown to give significantly inferior intake valve deposit weights (Average 127.9 and 105.2 mg, respectively) compared with the directly equivalent materials derived from PIB of Mn 1300 (Average 72.2 and 35.1 mg, respectively) .
- US Patent 5,478,367 discloses diesel fuel compositions containing certain macrocyclic polyamines derived from reaction of polyisobutylene succinic anhydride with certain polyamines, for reduction of particulate emissions on combustion.
- the diesel fuel used in the examples was a high-sulphur fuel (sulphur content of 0.23%w, i.e. 2,300 ppmw).
- the macrocyclic polyamines were characterised by their IR spectra having four peaks between 1900 and 1500 wave numbers. This is contrasted with the IR spectra of uncyclised equivalents, which only have three peaks in this region (Column 9, lines 16 to 22) .
- WO 94 20593 discloses a low emission diesel fuel having a cetane number in the range of 50 to 60, which comprises:- (i) a straight run hydrocarbon distillate having an initial boiling point in the range of 170°C to 190°C, an end point not higher than 315°C, a sulphur content of less than 0.1 wt percent (preferably sulphur content from 0.005 to 0.05%w, i.e. 50 to 500 ppmw) and aromatics content of 18 to 30 wt . percent, a maximum specific gravity of 0.83 at 15°C and an API gravity of 38 to 43, and
- an additive package comprising a detergent, a friction reducing additive and a cetane number improver.
- a detergent a friction reducing additive
- a cetane number improver two base fuels are used, one of sulphur content 0.01%w (100 ppmw) and one of 0.06%w (600 ppmw).
- the polyisobutylene succinimide detergent used in the examples is not specifically identified, but the general description does specifically state (Page 6, lines 10 to 14) that a
- preferred detergent is a polybutenyl bis (succinimide) produced from a polybutenyl succinic anhydride and tetraethylene pentamine (2:1 ratio, pb mol . wt . about 1200) in combination with ethylene diamine tetraacetic acid.
- WO 9623855 discusses in detail the lubricity problems of low-sulphur diesel fuels and discloses a fuel oil composition comprising a major amount of a fuel oil containing not more than 0.05% by weight of sulphur (i.e. 500 ppmw) and having a 95% distillation point of not greater than 350°C, and a minor amount of an additive composition comprising: (a) an ashless dispersant comprising an acylated nitrogen compound, and (b) a carboxylic acid, or an ester of the carboxylic acid and an alcohol wherein the acid has from 2 to 50 carbon atoms and the alcohol has one or more carbon atoms.
- an additive composition comprising: (a) an ashless dispersant comprising an acylated nitrogen compound, and (b) a carboxylic acid, or an ester of the carboxylic acid and an alcohol wherein the acid has from 2 to 50 carbon atoms and the alcohol has one or more carbon atoms.
- Preferred acylated nitrogen compounds are those made by reacting a polyisobutenyl succinic anhydride with mixtures of ethylene polyamines.
- the ashless dispersant employed is described as a "succinimide ashless dispersant being the reaction product of 1.5 equivalents of PIBSA (polyisobutyl succinic anhydride, with polyisobutylene number average molecular weight of approximately 950, as measured by Gel Permeation Chromatography) with one equivalent of polyethylene polyamine mixture of average composition approximating to pentaethylene hexamine".
- WO 94 17160 (Exxon) describes the use of certain esters of a carboxyclic acid and an alcohol wherein the acid has fr.om 2 to 50 carbon atoms and the alcohol has one or more carbon atoms, particularly glycerol monooleate and di-isodecyl adipate, as additives for fuel oils for wear reduction in the injection system of a compression-ignition engine.
- US Patent 5,484,462 mentions dimerized linoleic acid as a commercially available lubricity agent for low sulphur diesel fuel (Col. 1, line 38), and itself provides aminoalkylmorpholines as fuel lubricity improvers.
- US Patent 5,490,864 describes certain dithiophosphoric diester-dialcohols as anti-wear lubricity additives for low-sulphur diesel fuels.
- the present Applicant's European Patent Application No. 96304975.4 filed 5 July 1996, (Applicant's ref. TS 7520 EPC) discloses that certain alkyl aromatic compounds having at least one carboxyl group attached to their aromatic nuclei can confer anti-wear lubricity effects when incorporated in fuel oil, especially low- sulphur diesel fuel.
- the alkyl aromatic compounds are those wherein at least one alkyl group of 6 to 30 carbon atoms is attached to an aromatic nucleus and at least one carboxyl group and optionally one or two hydroxyl groups are attached to the aromatic nucleus .
- Preferred alkyl aromatic compounds are alkyl benzoic acids or alkylsalicylic acids containing one or two alkyl groups, preferably of 6 to 30 carbon atoms, more preferably a Cg_20 alkyl group, advantageously a Cg-i ⁇ alkyl group.
- a fuel oil composition comprising a major proportion of a liquid hydrocarbon middle distillate fuel oil having a sulphur concentration of at most 0.05% by weight, and a minor proportion of a dispersant additive obtained by reacting, in a molar ratio A:B in the range 4:3 to 1:10, (A) a polyalkenyl derivative of monoethylenically unsaturated C4-C10 dicarboxylic acid material in which the number average molecular weight (M n ) of the polyalkenyl chain is in the range from 850 to 1150 with (B) a polyamine of general formula
- the present invention provides a fuel oil composition
- a fuel oil composition comprising a major proportion of a liquid hydrocarbon middle distillate fuel oil having a sulphur concentration of at most 0.05% by weight and a minor amount of an additive composition comprising a dispersant additive and a lubricity additive, wherein the dispersant additive is obtained by reacting, in a molar ratio A:B in the range 4:3 to 1:10, (A) a polyalkenyl derivative of monoethylenically unsaturated c 4 ⁇ c 10 dicarboxylic acid material in which the number average molecular weight (M n ) of the polyalkenyl chain is in the range from 850 to 1150 with (B) a polyamine of general formula H 2 N(CH 2 ) m -[NH(CH2) m ] n -NH2 (I) where m is in the range from 2 to 4 and n is in the range from 1 to 6.
- the middle distillate fuel oil is derived from petroleum and will typically have a boiling range in the range 100°C to 500°C, e.g. 150°C to 400°C.
- Such petroleum-derived fuel oils may comprise atmospheric distillate or vacuum distillate, or cracked gas oil or a blend in any proportion of straight run and thermally and/or catalytically cracked distillates.
- Preferred fuel oil compositions of the invention are diesel fuel compositions . Diesel fuels typically have initial distillation temperature about 160°C and final distillation temperature of 290-360°C, depending on fuel grade and use.
- the fuel oil itself may be an additised (additive- containing) oil or an unadditised (additive-free) oil.
- the fuel oil is an additised oil, it will contain minor amounts of one or more additives, e.g. one or more additives selected from anti-static agents, pipeline drag reducers, flow improvers (e.g. ethylene/vinyl acetate copolymers or acrylate/maleic anhydride copolymers) and wax anti-settling agents (e.g. those commercially available under the Trade Marks "PARAFLOW” (e.g. "PARAFLOW” 450; ex Paramins),
- additives selected from anti-static agents, pipeline drag reducers, flow improvers (e.g. ethylene/vinyl acetate copolymers or acrylate/maleic anhydride copolymers) and wax anti-settling agents (e.g. those commercially available under the Trade Marks "PARAFLOW” (e.g. "PARAFLOW” 450; ex Paramins),
- additives selected from anti-static agents, pipeline drag reducers, flow improvers (e.g. ethylene/vinyl
- OCTEL e.g. "OCTEL” W 5000; ex Octel
- DODIFLOW e.g. DODIFLOW v 3958; ex Hoechst
- the fuel oil has a sulphur content of at most 0.05% by weight (500 ppmw) ("ppmw" is parts per million by weight) .
- Advantageous compositions of the invention are also attained when the sulphur content of the fuel oil is below 0.005 % by weight (50 ppmw) or even below 0.001% by weight (10 ppmw) .
- the polyalkenyl derivatives of monoethylenically unsaturated C4-C10 dicarboxylic acid material are known compounds or can be prepared by processes analogous to known processes.
- a derivative may conveniently be prepared by mixing a polyalkene with a specified amount of a monoethylenically unsaturated c 4 ⁇ "Cl0 dicarboxylic acid material and passing chlorine through the mixture, e.g. as described in GB-A-949, 981.
- the derivative may be prepared by reacting thermally at an appropriate temperature the polyalkene with a specified amount of the dicarboxylic acid material, e.g. as described in GB-A-1, 83, 729.
- a particularly advantageous process for preparing the derivative involves reacting the polyalkene with the dicarboxylic acid material in mol ratio dicarboxylic acid material :polyalkene greater than 1:1, at a temperature in the range 150 to 260°C, if desired in the presence of a polyaddition-inhibiting amount of a sulphonic acid, as described in EP-A-542 , 380.
- the polyalkene may conveniently be a homopolymer or copolymer, for example of at least one C2 _ C _Q monoolefin.
- the polyalkene is a polymer of at least one C2-C5 monoolefin, e.g. an ethylene- propylene copolymer.
- the monoolefin is preferably a C3-C4 olefin and preferred polyalkenes derived therefrom include polyisobutylenes and atactic or isotactic propylene oligomers.
- the monoolefin is most preferably isobutylene, so polyisobutylenes are the preferred form of polyalkene.
- suitable commercial polyisobutylenes are those sold by BP under the trade marks “HYVIS 10", “NAPVIS 10” and “ULTRAVIS 10", that sold by Exxon under the trade mark “PARAPOL 950", that sold by BASF under the trade mark “GLISSOPAL 1000" and that sold by Amoco under the trade mark "INDOPOL H 100".
- M n The number average molecular weight, of polyalkenes may be determined by several techniques which give closely similar results. Conveniently, M n may be determined for examples by modern gel permeation chromatography (GPC) , e.g. as described for example in W.W. Yau, J.J. Kirkland and D.D. Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979.
- GPC gel permeation chromatography
- the number average molecular weight of the polyalkenyl chain is in the range from 850 to 1150, preferably 850 to 1000.
- C4-C 1 C) dicarboxylic acid materials see for example
- US-A-4, 086,251 and US-A- , 235, 786) may for example be anhydrides, e.g. of C4-C5 dicarboxylic acids such as maleic acid, citraconic acid (methylmaleic acid) , itaconic acid (methylene succinic acid) and ethylmaleic acid.
- the C -C10 dicarboxylic acid material is preferably maleic anhydride.
- the polyalkenyl derivative will be a polyalkenyl succinic acid derivative.
- the ratio of dicarboxylic acid moieties per polyalkenyl chain (referred to as “succination ratio" when the dicarboxylic acid material is maleic anhydride) , r, may readily be determined by a procedure which will be described later, in the examples. "r” is preferably not greater than 1.2:1.
- polyamines of formula I above include diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptamine, tripropylene tetramine, and corresponding commercial mixtures such as "Polyamine H", "Polyamine 400" and "Polyamine S”.
- n is in the range 1 to 3.
- m is 2, so the preferred polyamines are polyethyleneamines .
- the molar ratio A:B is preferably less than 6:5, preferably in the range 6:5 to 1:2. Where excess polyamine is employed, unreacted amine may conveniently be removed by evaporation or by washing, e.g. with aqueous medium such as a methanol/water mixture.
- the dispersant additive are generally mixtures of amide and imide species, as demonstrated by infra-red spectroscopy.
- the dispersant additive is preferably present in an amount in the range of from 10 to 400 ppmw, more preferably 40 to 200 ppmw, active matter based on total composition .
- Fuel oil compositions of the present invention preferably additionally contain a lubricity additive in an amount in the range from 50 to 500 ppmw based on total composition.
- the lubricity additive may be any lubricity additive, e.g. as described above.
- Commercial lubricity additives include those available as EC 831 (ex Paramins), "HITEC” (trade mark) E580 (ex Ethyl Corporation) and "PARADYNE” (trade mark) 655 (ex Exxon Chemical Ltd) .
- the present invention further provides a process for the preparation of a fuel oil composition according to the invention, as defined above, which comprises admixing the dispersant additive or an additive concentrate containing the dispersant additive with the fuel oil.
- Additive concentrates suitable for incorporating in the fuel oil compositions will contain the dispersant additive, preferably together with the lubricity additive, and a fuel-compatible diluent, which may be a carrier oil (e.g. a mineral oil), a polyether, which may be capped or uncapped, a non-polar solvent such as toluene, xylene, white spirits and those sold by .member companies of the Royal Dutch/Shell Group under the Trade Mark "SHELLSOL”, and/or a polar solvent such as esters and, in particular, alcohols, e.g.
- a fuel-compatible diluent which may be a carrier oil (e.g. a mineral oil), a polyether, which may be capped or uncapped, a non-polar solvent such as toluene, xylene, white spirits and those sold by .member companies of the Royal Dutch/Shell Group under the Trade Mark "SHELLSOL”, and/or a polar solvent such as esters and, in
- hexanol 2- ethylhexanol, decanol, isotridecanol and alcohol mixtures such as those sold by member companies of the Royal Dutch/Shell Group under the Trade Mark “LINEVOL”, especially "LINEVOL” 79 alcohol which is a mixture of C7-.9 primary alcohols, or the C]_2-14 alcohol mixture commercially available from Sidobre Sinnova, France under the Trade Mark “SIPOL”.
- LINEVOL especially "LINEVOL” 79 alcohol which is a mixture of C7-.9 primary alcohols, or the C]_2-14 alcohol mixture commercially available from Sidobre Sinnova, France under the Trade Mark “SIPOL”.
- Additive concentrates and fuel oil compositions prepared therefrom may further contain additional additives such as dehazers, e.g. alkoxylated phenol formaldehyde polymers such as those commercially available as “NALCO” (trade mark) EC5462A (formerly 7D07) (ex Nalco) , and “TOLAD” (trade mark) 2683 (ex Petrolite) ; anti-foaming agents (e.g.
- RC 4801 a propane-1, 2-diol semiester of tetrapropenyl succinic acid, or polyhydric alcohol esters of a succinic acid derivative, the succinic acid derivative having on at least one of its alpha-carbon atoms an unsubstituted or substituted aliphatic hydrocarbon group containing from 20 to 500 carbon atoms, e.g. the pentaerythritol diester of polyisobutylene-substituted succinic acid) , reodorants, anti-wear additives; anti-oxidants (e.g.
- phenolics such as 2, 6-di-tert-butylphenol, or phenylenediamines such as N, N ' -di-sec-butyl-p- phenylenediamine) ; and metal deactivators .
- the (active matter) concentration of each additional additive in the diesel fuel is preferably up to 1 percent by weight, more preferably in the range from 5 to 1000 ppmw (parts per million by weight of the diesel fuel) . advantageously 75 to 300 ppmw e.g. 95 to 150 ppmw.
- the (active matter) concentration of the dehazer in the diesel fuel is preferably in the range from 1 to 20 ppmw, more preferably from 1 to 15 ppmw, still more preferably from 1 to 10 ppmw and advantageously from 1 to 5 ppmw.
- the (active matter) concentrations of other additives are each preferably in the range from 0 to 20 ppmw, more preferably from 0 to 10 ppmw.
- the (active matter) concentration of the ignition improver in the diesel fuel is preferably in the range from 0 to 600 ppmw and more preferably from 0 to 500 ppmw. If an ignition improver is incorporated into the diesel fuel, it may conveniently be used in an amount of 300 to 500 ppmw.
- the invention further provides a method of operating a compression-ignition engine which comprises introducing into the combustion chambers of said engine a fuel composition according to the invention as defined above.
- a compression-ignition engine which comprises introducing into the combustion chambers of said engine a fuel composition according to the invention as defined above.
- AV denotes acid value, and this was determined using a “Metrohm 670” (trade mark) potentiometric titrometer according to a method based upon ASTM D 664-
- TBN denotes total basic nitrogen, and this was determined using a “Metrohm 670” (trade mark) potentiometric titrometer according to a method based upon ASTM D 2896 with modified solvent system (75% w toluene, 12.5% w acetonitrile, 12.5% w acetic acid);
- AM denotes active matter content, and this was determined by separating inactive material from the desired active matter in obtained product on an aluminium oxide column using diethyl ether as eluant, and is expressed as a percentage relative to the obtained product.
- “Succination ratio”, r is the ratio of succinic anhydride moieties per polyisobutenyl chain, in the reaction product from reaction of polyisobutylene with maleic anhydride, and is calculated from the following expression :
- M n Molecular weight of the dicarboxylic acid material (98 for maleic anhydride)
- the first method (1) involved reaction of polyisobutylene (PIB) with maleic anhydride (MALA) in mol ratio PIB:MALA of 1:1.5 for 6 hours in an autoclave under pressure. Unreacted MALA was then removed by vacuum distillation. The residue was diluted with about 20% w mineral oil ("HVI 60" base oil - a bright and clear high viscosity index base oil having viscosity at 100°C of 4.4 to 4.9 mm 2 /s (ASTM D 445)) and filtered to remove insoluble material.
- the second method (2) involved heating PIB with stirring to 210°C in a three- necked flask equipped with a condenser and overhead stirrer.
- MALA was added over 30 minutes to a final mol ratio PIB:MALA of 1:3, and the resulting mixture was stirred at 210°C for 8 hours. Unreacted MALA was removed by vacuum distillation, the residue was diluted with n-heptane, filtered to remove insoluble material, and evaporated under vacuum to remove the n-heptane.
- Dispersant additive test materials were prepared according to one or other of the following procedures :-
- Method A (with reference to Test Material 1 of Table 2 below) Into a three-necked flask equipped with an overhead mechanical stirrer, Dean and Stark trap, reflux condenser and thermometer was introduced a solution of tetraethylenepentamine (TEPA) (34.7 g, 0.184 mol) in xylene (150 ml) . The solution was stirred and heated in an oil-bath to 90°C and a solution of polyisobutenylsuccinic anhydride (PIBSA A) (233g, 0.125 mol at 56.8% active matter) in xylene (200 ml) was added dropwise over 1.5 hours. After addition was complete, the reaction mixture was heated at reflux temperature for 4 hours with removal of water formed from the reaction. The amount of water collected was 2 ml (theoretical amount 2.25 ml) .
- TEPA tetraethylenepentamine
- PIBSA A polyisobutenylsuccinic anhydride
- PIBSA A polyiso- butenylsuccinic anhydride
- the dispersant additive test materials of Table 2 were diluted to an active matter concentration of 27% w by addition of "SHELLSOL R" (Trade Mark) solvent.
- SHELLSOL R is an aromatic hydrocarbon solvent (74% aromatic) of boiling range 205 to 270°C and average molecular weight 156. Treat rates in diesel fuels of the resulting dispersant solutions of 200 ppmw and
- 250 ppmw then correspond respectively to 54 ppmw and 68 ppmw of active matter.
- Additive concentrate compositions for low sulphur diesel fuel were prepared by mixing (A) 200 parts by weight or (B) 250 parts by weight (pbw) of the above dispersant solutions with 300 pbw of 2-ethylhexyl nitrate (EHN) ignition improver, 5 pbw of an anti-rust agent, 5 pbw of an antifoaming agent, 5 pbw of a dehazer, 100 pbw of an alcohol solvent and 100 pbw of a lubricity additive.
- EHN 2-ethylhexyl nitrate
- the specific anti-rust agent used was a hydroxypropyl ester of tetrapropenyl succinic acid (propane-1, 2-diol semiester of tetrapropenyl succinic acid) (c.f. Example IV of UK Patent 1,306,233).
- the antifoaming agent was a silicone antifoam additive sold by OSi Specialties (UK) Ltd, Harefield, UK under the trade designation "SAG TP-325" ("SAG” is a trade mark) .
- the dehazer was an alkoxylated phenol formaldehyde polymer dehazer available ex Nalco as "NALCO” EC5462A (formerly 7D07) (trade mark).
- the alcohol solvent was a blend of C ⁇ - _) primary alcohols available from member companies of the Royal Dutch/Shell group as "LINEVOL 79" (trade mark) .
- the lubricity agent used was a synthetic ester- containing lubricity additive available ex Exxon Chemical Ltd, Fareham, UK, under the trade designation "PARADYNE 655" ("PARADYNE” is a trade mark) .
- additive concentrate compositions for conventional (high sulphur) diesel fuel were prepared by mixing (A) 200 pbw or (B) 250 pbw of the above dispersant solutions with 300 pbw EHN, 5 pbw of the above anti-rust agent, 5 pbw of the above antifoaming agent, 5 pbw of the above dehazer and 25 pbw of the above alcohol solvent.
- each additive concentrate composition was added to base fuel in amounts such that each "part by weight" above became 1 ppmw of fuel formulation, e.g. each fuel formulation contained 300 ppmw EHN.
- Steady-state injector nozzle fouling tests were performed according to the following method, employing a four cylinder VW Passat AAZ 1.9 TD (turbo diesel) IDI (indirect injection) diesel engine of 1896 cc displacement, equipped with a Bosch fuel injection system employing injector nozzles of type DNO SD 308.
- the engine was warmed up at 1500 rpm engine speed and 25 Nm dynamometer load for 20 minutes. The engine speed was then raised to 2000 rpm and the dynamometer load was increased to 90 Nm over 15 seconds, and the engine was run at that speed and load for 3 hours.
- a fouling index was generated from measurements of air flow through the injector nozzles, assessments being made on the new nozzles, before the test (Flow Clean), and afterwards on the fouled nozzles (Flow
- Air flow was measured in a Ricardo air-flow rig according to ISO 4010, measurements being recorded at needle lifts of 0.1, 0.2 and 0.3 mm, with a vacuum pressure 6Q0 mBar (60,000 Pa).
- a fouling number for one nozzle was calculated by averaging the three values of F obtained at the three different needle lifts.
- the fouling index ( FI ) was obtained by averaging the fouling numbers from all four nozzles .
- Tests were performed on low-sulphur fuel formulations as described above, containing 200 ppmw and 250 ppmw of dispersant solution of test material 1 (Examples 1 and 2), and for comparison purpose of material Comp. A (Comparative Examples I and II) . Comparative tests were also performed on high-sulphur fuel formulations as described above, containing 200 ppmw and 250 ppmw of dispersant solution of test material 1 (Comparative Examples III and IV) and of material Comp. A (Comparative Examples V and VI) . Values for base fuel are given as Comparative Examples VII and VIII.
- Comp. Ill and Comp. IV correspond to the fuels described on page 5 lines 28 to 52 of UK Patent Specification No. 960,493, wherein a polyisobutenyl mono-succinimide derived from PIB of Mn 950 and TEPA as amine was tested at a concentration of 200 ppmw in a high-sulphur fuel of cetane number 36 and sulphur content 0.5% (5000 ppmw) .
- Additive concentrate compositions were prepared as described about except that different quantities of the dispersant solutions were used, 300 pbw of "SHELLSOL R” solvent was used in place of the 100 pbw alcohol solvent, the antifoaming agent was a silicone antifoam agent sold by Th. Goldschmidt A.G., Essen, Germany, under the trade designation “TEGOPREN 5851” ("TEGOPREN” is a trade mark) , and the lubricity agent was a fatty acid dimer based material available ex Ethyl Petroleum Additives Inc., St. Louis, USA under the trade designation "HITEC E580” (“HITEC” is a trade mark) .
- Test fuel formulations were prepared on the same basis as above, using the low sulphur fuel LS as base fuel. Using the resulting fuels, steady-state injector nozzle fouling tests were performed using a Fiat IDI 1929 cc , type 149 Al.OOO, diesel engine as used in Fiat Regata diesel automobiles, equipped with a Bosch injector system employing injector nozzles of type DN 125D 1750.
- the engine was warmed up at 1500 rpm engine speed and 25 Nm dynamometer load for 20 mins . Injector nozzles were then changed to test nozzles. The engine was then run at 2700 rpm and 75 Nm for
- Performance of each diesel fuel was assessed qualitatively by air-flow measurement of fouling levels produced in the engine's injector nozzles.
- the nozzles, of type Bosch DN 12 SD 1750, were placed in a Ricardo air-flow rig according to ISO 4010, and airflow measurements were recorded at needle lifts of 0.2, 0.2 and 0.3 mm, with a vacuum pressure 600m Bar (60, 000 Pa) .
- Fouling Index values were derived from the air-flow measurements by the calculation method described for Examples 1 and 2. Results of these tests are given in Table 5 following, in which the values given in ppmw for treat rate also represent the parts by weight used in the additive concentrate compositions.
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Abstract
Description
Claims
Priority Applications (1)
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EP98917104A EP0968259B1 (en) | 1997-03-21 | 1998-03-20 | Fuel oil compositions |
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PCT/EP1998/001895 WO1998042808A1 (en) | 1997-03-21 | 1998-03-20 | Fuel oil compositions |
EP98917104A EP0968259B1 (en) | 1997-03-21 | 1998-03-20 | Fuel oil compositions |
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Also Published As
Publication number | Publication date |
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KR20010005606A (en) | 2001-01-15 |
EP0968259B1 (en) | 2002-08-28 |
WO1998042808A1 (en) | 1998-10-01 |
KR100509082B1 (en) | 2005-08-18 |
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