EP0968259B1 - Brennölzusammensetzungen - Google Patents

Brennölzusammensetzungen Download PDF

Info

Publication number
EP0968259B1
EP0968259B1 EP98917104A EP98917104A EP0968259B1 EP 0968259 B1 EP0968259 B1 EP 0968259B1 EP 98917104 A EP98917104 A EP 98917104A EP 98917104 A EP98917104 A EP 98917104A EP 0968259 B1 EP0968259 B1 EP 0968259B1
Authority
EP
European Patent Office
Prior art keywords
range
fuel
ppmw
composition according
additive
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.)
Expired - Lifetime
Application number
EP98917104A
Other languages
English (en)
French (fr)
Other versions
EP0968259A1 (de
Inventor
Michael John Grundy
Michael Pearson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Infineum Holdings BV
Original Assignee
Infineum Holdings BV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=26070306&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0968259(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Infineum Holdings BV filed Critical Infineum Holdings BV
Priority to EP98917104A priority Critical patent/EP0968259B1/de
Publication of EP0968259A1 publication Critical patent/EP0968259A1/de
Application granted granted Critical
Publication of EP0968259B1 publication Critical patent/EP0968259B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • 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)
    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10L1/1608—Well defined compounds, e.g. hexane, benzene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/1811—Organic compounds containing oxygen peroxides; ozonides
    • 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
    • C10L1/182—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
    • 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
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • 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
    • 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
    • C10L1/188—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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C10L1/198—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
    • 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
    • C10L1/198—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
    • 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
    • C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
    • C10L1/231—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites
    • 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
    • C10L1/28—Organic compounds containing silicon
    • C10L1/285—Organic compounds containing silicon macromolecular compounds

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.
  • 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).
  • the single example of the preparation of such a succinimide is based on polyisobutylene of molecular weight about 1000, the molar ratio of the alkenyl anhydride to the tetraethylene pentamine being 1:1, and the molar ratio of the succinic acid to the polyisobutylene being 1:1.
  • This product is evaluated in gasoline and in a high-sulphur diesel fuel having a sulphur content of 0.5% by wt. 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 H 2 N-(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-557 516 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:
  • 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:
  • 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:
  • WO-A-96/23855 discloses that suitable acylated nitrogen compounds for use in the invention are disclosed in US-A-3 310 492. The latter exemplifies the preparation of acylated nitrogen compounds from polyalkenyl substituted succinic acid but does not disclose the molar ratio of the dicarboxylic acid moieties per polyalkenyl chain.
  • WO 95 33805 (Exxon) describes the use of cold flow improvers to enhance lubricity of low-sulphur fuels.
  • WO 94 17160 (Exxon) describes the use of certain esters of a carboxyclic acid and an alcohol wherein the acid has from 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.
  • WO-A-98/01516 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 C 8-20 alkyl group, advantageously a C 8-18 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 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 and the ratio of dicarboxylic moieties per polyalkenyl chain is not greater than 1.2 : 1, with (B) a polyamine of general formula H 2 N(CH 2 ) m -[NH(CH 2 ) m ] n -NH 2 where m is in the range from 2 to 4 and n is in the range from 1 to 6.
  • 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(CH 2 ) m ] n -NH 2 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. If 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), "OCTEL” (e.g. "OCTEL” W 5000; ex Octel) and "DODIFLOW” (e.g. DODIFLOW” v 3958; ex Hoechst).
  • additives e.g. one or more additives selected from anti-static agents, pipeline drag reducers, flow improvers (e.g. ethylene/vinyl
  • the fuel oil has a sulphur content of at most 0.05% by weight (500 ppmw) ("ppmw" is parts per million by weight).
  • 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 C 4 -C 10 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 -C 10 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-1,483,729.
  • 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 C 2 -C 10 monoolefin.
  • the polyalkene is a polymer of at least one C 2 -C 5 monoolefin, e.g. an ethylenepropylene copolymer.
  • the monoolefin is preferably a C 3 -C 4 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.
  • C 4 -C 10 dicarboxylic acid materials may for example be anhydrides, e.g. of C 4 -C 6 dicarboxylic acids such as maleic acid, citraconic acid (methylmaleic acid), itaconic acid (methylene succinic acid) and ethylmaleic acid.
  • the C 4 -C 10 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 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 particular, alcohols
  • 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 C 7-9 primary alcohols, or the C 12-14 alcohol mixture commercially available from Sidobre Sinnova, France under the Trade Mark “SIPOL”.
  • LINEVOL especially "LINEVOL” 79 alcohol which is a mixture of C 7-9 primary alcohols, or the C 12-14 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 7DO7) (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.
  • phenolics such as 2,6-di-tert-butylphenol, or phenylenediamines such as N,N'-di-sec-but
  • 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.
  • test materials were prepared as follows.
  • AV denotes acid value, and this was determined using a "Metrohm 670" (trade mark) potentiometric titrometer according to a method based upon ASTM D 664-89 with modified solvent system (75% w toluene, 12.5% w acetonitrile, 12.5% w acetic acid);
  • 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.
  • M n values given for M n herein are determined by gel permeation chromatography, e.g. as described in W.W. Yan, J.J. Kirkland and D.D. Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979.
  • PIBSA Polyisobutenyl succinic 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.
  • HVI 60 base oil
  • ASTM D 445 a bright and clear high viscosity index base oil having viscosity at 100°C of 4.4 to 4.9 mm 2 /s
  • 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:-
  • the xylene solvent was removed using a rotary evaporator leaving a residue in the form of a brown oil. This oil was dissolved in 1 l of heptane and washed with 9:1 methanol/water mixture (3 x 300 ml) to remove excess amine. Again the solvent was removed using the rotary evaporator to yield 264 g of desired product.
  • polyisobutenylsuccinic anhydride (PIBSA A) (1000 g, 0.536 mol at 56.8 % active matter). This was heated to 140°C with stirring, and TEPA (101.46 g, 0.536 mol) was added dropwise over 10 minutes. After addition was complete, the temperature of the reaction mixture was raised to 160°C and maintained at 160°C for 2 hours. Volatile materials were removed using a rotary evaporator to yield the desired product as 1136 g of brown liquid.
  • PIBSA A polyisobutenylsuccinic anhydride
  • diethylenetriamine DETA
  • PIBSA B polyisobutenyl succinic anhydride
  • the reaction mixture was heated to 160°C and maintained at 160°C for a further 2 hours before cooling and dissolving in 1 l of heptane.
  • the solution was washed with a 9:1 methanol/water mixture (3 x 300 ml) to remove excess amine.
  • the solvent was removed using a rotary evaporator to yield the desired product as 91 g of brown oil.
  • 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 7DO7) (trade mark).
  • the alcohol solvent was a blend of C 7-9 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.
  • the base fuels employed were as follows: Low-sulphur fuel High-sulphur fuel Density (kg/l) at 15°C (ASTM D 4052) 0.827 0.853 Sulphur (ppmw) (IP 373) 375 1800 Distillation, degrees C (ASTM D 86) IBP 155.5 174 10% 192.5 226 20% 210.5 249 50% 269 286 90% 343 340 95% 356 355 FBP 365 367 Cetane No. (ASTM D 613) 51.7 50.0
  • 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 Fouled). 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 600 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. III 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).
  • dispersant additives of the invention were very significantly superior to otherwise similar material which was formed by reaction with an amine of different structure, viz. 3-dimethylaminopropylamine (DAT).
  • DAT 3-dimethylaminopropylamine
  • 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.
  • 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 8.5 hours, after which the engine was switched off. Coolant oil/water temperatures were maintained at 90 ⁇ 4°C.
  • 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 air-flow 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Lubricants (AREA)

Claims (10)

  1. Treib- oder Brennstoffölzusammensetzung, die einen größeren Anteil flüssiges Kohlenwasserstoffmitteldestillattreib- oder -brennstofföl mit einer Schwefelkonzentration von höchstens 0,05 Gew.-% und einen kleineren Anteil Dispergieradditiv umfasst, das durch Umsetzung von (A) Polyalkenylderivat von monoethylenisch ungesättigtem C4- bis C10-Dicarbonsäurematerial, bei dem das durchschnittliche Molekulargewicht (Zahlenmittel, Mn) der Polyalkenylkette im Bereich von 850 bis 1150 liegt und das Verhältnis von Dicarbonsäuregruppen pro Polyalkenylkette nicht größer als 1,2 : 1 ist, mit (B) Polyamin der allgemeinen Formel H2N(CH2)m- (NH(CH2)m)n-NH2 wobei m im Bereich von 2 bis 4 liegt und n im Bereich von 1 bis 6 liegt, in einem Molverhältnis A:B im Bereich von 4 : 3 bis 1 : 10 erhalten wird.
  2. Zusammensetzung nach Anspruch 1, bei der die Polyalkenylkette abgeleitet ist von Polymer aus mindestens einem C2bis C5-Monoolefin.
  3. Zusammensetzung nach Anspruch 2, bei der das Monoolefin Isobutylen ist.
  4. Zusammensetzung nach einem der Ansprüche 1 bis 3, bei der n im Bereich von 1 bis 3 liegt.
  5. Zusammensetzung nach einem der Ansprüche 1 bis 4, bei der das Molverhältnis A : B im Bereich von 6 : 5 bis 1 : 2 liegt.
  6. Zusammensetzung nach einem der Ansprüche 1 bis 5, bei der die Menge von Dispergieradditiv im Bereich von 10 bis 400 Gew.-ppm aktiver Bestandteil liegt, bezogen auf die Gesamtzusammensetzung.
  7. Zusammensetzung nach einem der Ansprüche 1 bis 6, bei der die Menge von Dispergieradditiv im Bereich von 40 bis 200 Gew.-ppm aktiver Bestandteil liegt, bezogen auf die Gesamtzusammensetzung.
  8. Zusammensetzung nach einem der Ansprüche 1 bis 7, die zusätzlich Schmieradditiv in einer Menge im Bereich von 50 bis 500 Gew.-ppm enthält, bezogen auf die Gesamtzusammensetzung.
  9. Verfahren zur Herstellung einer Treib- oder Brennstoffölzusammensetzung gemäß einem der Ansprüche 1 bis 8, bei dem das Dispergieradditiv oder Additivkonzentrat, das das Dispergieradditiv enthält, mit dem Treib- oder Brennstofföl gemischt wird.
  10. Verfahren zum Betreiben eines Motors mit Kompressionszündung, bei dem eine Treib- oder Brennstoffzusammensetzung gemäß einem der Ansprüche 1 bis 8 in die Verbrennungskammer des Motors eingebracht wird.
EP98917104A 1997-03-21 1998-03-20 Brennölzusammensetzungen Expired - Lifetime EP0968259B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP98917104A EP0968259B1 (de) 1997-03-21 1998-03-20 Brennölzusammensetzungen

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP97301931 1997-03-21
EP97301931 1997-03-21
EP98917104A EP0968259B1 (de) 1997-03-21 1998-03-20 Brennölzusammensetzungen
PCT/EP1998/001895 WO1998042808A1 (en) 1997-03-21 1998-03-20 Fuel oil compositions

Publications (2)

Publication Number Publication Date
EP0968259A1 EP0968259A1 (de) 2000-01-05
EP0968259B1 true EP0968259B1 (de) 2002-08-28

Family

ID=26070306

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98917104A Expired - Lifetime EP0968259B1 (de) 1997-03-21 1998-03-20 Brennölzusammensetzungen

Country Status (3)

Country Link
EP (1) EP0968259B1 (de)
KR (1) KR100509082B1 (de)
WO (1) WO1998042808A1 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104789279A (zh) * 2015-04-29 2015-07-22 安徽中禄新能源科技开发有限公司 一种高清洁压燃式内燃机用醇氢油及其制备方法
US10829706B2 (en) 2017-07-19 2020-11-10 Sabic Global Technologies B.V. Cetane-boosting fuel additives, method of manufacture, and uses thereof
US11008525B2 (en) 2017-03-22 2021-05-18 Sabic Global Technologies B.V. Octane-boosting fuel additives, method of manufacture, and uses thereof

Families Citing this family (67)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010042033A (ko) * 1998-06-15 2001-05-25 도미나가 가즈토 연료유용 첨가제 및 연료유 조성물
US6200359B1 (en) 1998-12-23 2001-03-13 Shell Oil Company Fuel oil composition
DE19948111A1 (de) 1999-10-06 2001-04-12 Basf Ag Verfahren zur Herstellung Polyisobutenphenol-haltiger Mannichaddukte
DE19948114A1 (de) 1999-10-06 2001-04-12 Basf Ag Verfahren zur Herstellung Polyisobutenphenol-haltiger Mannichaddukte
AU5498301A (en) * 2000-05-12 2001-11-20 Associated Octel Company Limited, The Diesel fuel stabiliser
CA2437945A1 (en) * 2001-02-14 2002-12-27 The Lubrizol Corporation Fuel additive composition and fuel composition and method thereof
DE10123553A1 (de) * 2001-05-15 2002-11-21 Basf Ag Verfahren zur Herstellung von Polyalkenylsuccinimidprodukten, neue Polyalkenylsuccinimidprodukte mit verbesserten Eigenschaften, Zwischenprodukte und Verwendungen
GB0127953D0 (en) * 2001-11-21 2002-01-16 Shell Int Research Diesel fuel compositions
MY140297A (en) 2002-10-18 2009-12-31 Shell Int Research A fuel composition comprising a base fuel, a fischer-tropsch derived gas oil and an oxygenate
AR041930A1 (es) 2002-11-13 2005-06-01 Shell Int Research Composiciones de combustible diesel
EP1664248B1 (de) 2003-09-03 2011-12-21 Shell Internationale Research Maatschappij B.V. Kraftstoffzusammensetzungen
AU2004295472B2 (en) 2003-12-01 2009-02-26 Shell Internationale Research Maatschappij B.V. Power increase and increase in acceleration performance of a compression ignition engine provided by the diesel fuel composition
US7402186B2 (en) 2004-02-09 2008-07-22 The Lubrizol Corporation Fuel composition containing a medium substantially free of sulphur and process thereof
WO2006063161A2 (en) * 2004-12-09 2006-06-15 The Lubrizol Corporation Process of preparation of an additive and its use
EP3406692A1 (de) 2005-06-16 2018-11-28 The Lubrizol Corporation Brennstoffzusammensetzung enthaltend eines quaternären ammoniaksalzreinigungsmittel
BRPI0615192A2 (pt) 2005-08-22 2011-05-10 Shell Int Research combustÍvel diesel, e, mÉtodos para operar um motor a diesel e para reduzir a emissço de àxidos de nitrogÊnio
AR059751A1 (es) 2006-03-10 2008-04-23 Shell Int Research Composiciones de combustible diesel
EP2007858B2 (de) 2006-04-18 2022-03-16 Shell Internationale Research Maatschappij B.V. Brennstoffzusammensetzungen
US20070283618A1 (en) * 2006-06-09 2007-12-13 Malfer Dennis J Diesel detergents
CA2681312C (en) * 2007-04-04 2015-10-27 The Lubrizol Corporation A synergistic combination of a hindered phenol and nitrogen containing detergent for biodiesel fuel to improve oxidative stability
US7960322B2 (en) 2007-10-26 2011-06-14 Chevron Oronite Company Llc Lubricating oil compositions comprising a biodiesel fuel and an antioxidant
US7838474B2 (en) 2007-10-31 2010-11-23 Chevron Oronite Company Llc Lubricating oil compositions comprising a biodiesel fuel and a detergent
US8198225B2 (en) 2007-11-29 2012-06-12 Chevron Oronite Company Llc Sulfurized metal alkyl phenate compositions having a low alkyl phenol content
US8152869B2 (en) 2007-12-20 2012-04-10 Shell Oil Company Fuel compositions
JP2011508000A (ja) 2007-12-20 2011-03-10 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ 燃料組成物
EP2077315B1 (de) 2007-12-20 2012-10-31 Chevron Oronite Company LLC Schmierölzusammensetzungen mit einem Tetraalkyl-Naphtalen-1,8-Diamin-Antioxidant und einem Diarylamin-Antioxidant
EP2078743A1 (de) 2008-01-10 2009-07-15 Shell Internationale Researchmaatschappij B.V. Kraftstoffzusammensetzung
EP2078744A1 (de) 2008-01-10 2009-07-15 Shell Internationale Researchmaatschappij B.V. Kraftstoffzusammensetzungen
US8153570B2 (en) 2008-06-09 2012-04-10 The Lubrizol Corporation Quaternary ammonium salt detergents for use in lubricating compositions
US20100107482A1 (en) 2008-11-06 2010-05-06 Bennett Joshua J Conductivity-improving additives for fuel
EP2370553B1 (de) 2008-12-29 2013-07-24 Shell Internationale Research Maatschappij B.V. KRAFTSTOFFZUSAMMENSETZUNGEN enthaltend Tetrahydroquinolin
WO2010076303A1 (en) 2008-12-29 2010-07-08 Shell Internationale Research Maatschappij B.V. Fuel compositions
JP2013515802A (ja) 2009-12-24 2013-05-09 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ 液体燃料組成物
RU2012132488A (ru) 2009-12-29 2014-02-10 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Композиции жидких топлив
EP2371931B1 (de) 2010-03-23 2013-12-11 Shell Internationale Research Maatschappij B.V. Kraftstoffzusammensetzungen enthaltend Biodiesel und Fischer-Tropsch-Diesel
US9212320B2 (en) 2011-05-23 2015-12-15 Virent, Inc. Production of chemicals and fuels from biomass
US20140038303A1 (en) 2011-01-21 2014-02-06 Keith Reading Test kit and method for detection of additives in fuel compositions
US20120304531A1 (en) 2011-05-30 2012-12-06 Shell Oil Company Liquid fuel compositions
EP2748290A1 (de) 2011-09-06 2014-07-02 Shell Internationale Research Maatschappij B.V. Flüssigkraftstoffzusammensetzungen
CA2853293A1 (en) 2011-11-11 2013-05-16 The Procter & Gamble Company Fabric enhancers
US8641788B2 (en) 2011-12-07 2014-02-04 Igp Energy, Inc. Fuels and fuel additives comprising butanol and pentanol
EP2841537A1 (de) * 2012-04-24 2015-03-04 Basf Se Verwendung von zusätzen mit reinigungswirkung zur weiteren erhöhung der cetanzahl von brennstoffölen
DE102013112821A1 (de) 2012-11-30 2014-06-05 Shell Internationale Research Maatschappij B.V. Kraftstoffzusammensetzungen
TR201908686T4 (tr) 2012-12-21 2019-07-22 Shell Int Research Bir dizel yakıt bileşiminde bir organik güneş koruyucu bileşiklerin kullanımı.
CN105658774B (zh) 2013-10-24 2018-04-06 国际壳牌研究有限公司 液体燃料组合物
CN105814176B (zh) 2013-12-16 2017-08-15 国际壳牌研究有限公司 液体燃料组合物
EP2889361A1 (de) 2013-12-31 2015-07-01 Shell Internationale Research Maatschappij B.V. Dieselkraftstoffformulierung und Verwendung davon
EP2907867A1 (de) 2014-02-17 2015-08-19 Shell International Research Maatschappij B.V. Kraftstoffzusammensetzungen
US9057035B1 (en) 2014-02-17 2015-06-16 Shell Oil Company Fuel compositions
RU2733746C2 (ru) 2014-05-22 2020-10-06 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Топливные композиции
EP2949732B1 (de) 2014-05-28 2018-06-20 Shell International Research Maatschappij B.V. Verwendung einer oxanilid-verbindung in einer dieselkraftstoffzusammensetzung für den zweck der modifizierung der zündverzögerung und/oder der brenndauer
WO2016188858A1 (en) 2015-05-22 2016-12-01 Shell Internationale Research Maatschappij B.V. Fuel composition
CN107636127A (zh) 2015-05-22 2018-01-26 国际壳牌研究有限公司 燃料组合物
MY188997A (en) 2015-11-11 2022-01-17 Shell Int Research Process for preparing a diesel fuel composition
EP3184612A1 (de) 2015-12-21 2017-06-28 Shell Internationale Research Maatschappij B.V. Verfahren zur herstellung einer dieselkraftstoffzusammensetzung
MY191716A (en) 2016-02-05 2022-07-09 Shell Int Research Fuel composition
WO2017202735A1 (en) 2016-05-23 2017-11-30 Shell Internationale Research Maatschappij B.V. Use of a wax anti-settling additive in automotive fuel compositions
EP3464521B1 (de) 2016-05-26 2021-09-08 Shell Internationale Research Maatschappij B.V. Verwendung von kraftstoffzusammensetzungen zur reduzierung von ablagerungen
WO2018077976A1 (en) 2016-10-27 2018-05-03 Shell Internationale Research Maatschappij B.V. Process for preparing an automotive gasoil
WO2018206729A1 (en) 2017-05-11 2018-11-15 Shell Internationale Research Maatschappij B.V. Process for preparing an automotive gas oil fraction
WO2020070246A1 (en) 2018-10-05 2020-04-09 Shell Internationale Research Maatschappij B.V. Fuel compositions
EP3887489A1 (de) 2018-11-26 2021-10-06 Shell Internationale Research Maatschappij B.V. Kraftstoffzusammensetzungen
MX2021006634A (es) 2018-12-11 2021-07-07 Shell Int Research Uso y metodo para reducir sedimentos en motores de combustion interna de encendido por compresion.
KR20220042348A (ko) 2019-07-30 2022-04-05 쉘 인터내셔날 리써취 마트샤피지 비.브이. 안정성이 향상된 연료 조성물 및 이의 제조 방법
CN114717036A (zh) * 2021-01-06 2022-07-08 中国石油天然气股份有限公司 一种无灰分散剂的制备方法
JP2024515768A (ja) 2021-04-26 2024-04-10 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ 燃料組成物
MX2023012349A (es) 2021-04-26 2023-10-30 Shell Int Research Composiciones de combustible.

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL120517C (de) * 1960-12-16
US3310492A (en) * 1964-09-08 1967-03-21 Chevron Res Oils for two-cycle engines containing basic amino-containing detergents and aryl halides
US4482356A (en) * 1983-12-30 1984-11-13 Ethyl Corporation Diesel fuel containing alkenyl succinimide
US5089028A (en) * 1990-08-09 1992-02-18 Mobil Oil Corporation Deposit control additives and fuel compositions containing the same
EP0482253A1 (de) * 1990-10-23 1992-04-29 Ethyl Petroleum Additives Limited Umweltfreundliche Kraftstoffzusammensetzungen und Zusätze dafür
US5478367A (en) * 1991-10-11 1995-12-26 Exxon Chemical Patents Inc. Fuel oil compositions
AU668151B2 (en) * 1992-05-06 1996-04-26 Afton Chemical Corporation Composition for control of induction system deposits
NZ263659A (en) * 1993-03-05 1996-11-26 Mobil Oil Corp Low emission diesel fuel comprising hydrocarbon distillate and an additive package comprising a detergent, friction reducing additive and a cetane number improver
GB2279965A (en) * 1993-07-12 1995-01-18 Ethyl Petroleum Additives Ltd Additive compositions for control of deposits, exhaust emissions and/or fuel consumption in internal combustion engines
GB9502041D0 (en) * 1995-02-02 1995-03-22 Exxon Chemical Patents Inc Additives and fuel oil compositions

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104789279A (zh) * 2015-04-29 2015-07-22 安徽中禄新能源科技开发有限公司 一种高清洁压燃式内燃机用醇氢油及其制备方法
CN104789279B (zh) * 2015-04-29 2016-08-03 安徽中禄新能源科技开发有限公司 一种高清洁压燃式内燃机用醇氢油及其制备方法
US11008525B2 (en) 2017-03-22 2021-05-18 Sabic Global Technologies B.V. Octane-boosting fuel additives, method of manufacture, and uses thereof
US10829706B2 (en) 2017-07-19 2020-11-10 Sabic Global Technologies B.V. Cetane-boosting fuel additives, method of manufacture, and uses thereof

Also Published As

Publication number Publication date
KR100509082B1 (ko) 2005-08-18
WO1998042808A1 (en) 1998-10-01
EP0968259A1 (de) 2000-01-05
KR20010005606A (ko) 2001-01-15

Similar Documents

Publication Publication Date Title
EP0968259B1 (de) Brennölzusammensetzungen
EP1137745B1 (de) Brennstoffzusatz und diesen enthaltende brennstoffzusammensetzung
US6733550B1 (en) Fuel oil composition
EP0897382B1 (de) Alkoxyessigsäure-derivate
EP0984003B1 (de) Polyisobutansuccinimid Verbindungen und dieselben enthaltende Kraftstoffzusammentsetzungen
US20060168876A1 (en) Fuels compositions and methods for using same
US20080141580A1 (en) Fuel Oil Compositions
EP1057811B1 (de) Polyalkylpyrrolidine und diese enthaltende Kraftstoffzusammensetzungen
AU2006298847B2 (en) Fuel compositions
US6361573B1 (en) Fuel dispersants with enhanced lubricity
EP1274820B1 (de) Brennölzusammensetzungen
CA2389541C (en) Additive concentrate
EP0587250B1 (de) Benzinzusammensetzungen
CN115725348A (zh) 曼尼希基季铵盐燃料添加剂
KR20010112225A (ko) 연료 첨가제 및 이를 함유하는 연료 조성물

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19990920

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB IT NL

17Q First examination report despatched

Effective date: 20000511

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT NL

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 69807448

Country of ref document: DE

Date of ref document: 20021002

ET Fr: translation filed
PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

26 Opposition filed

Opponent name: BP OIL INTERNATIONAL LTD.

Effective date: 20030527

26 Opposition filed

Opponent name: BASF AKTIENGESELLSCHAFT

Effective date: 20030528

Opponent name: BP OIL INTERNATIONAL LTD.

Effective date: 20030527

NLR1 Nl: opposition has been filed with the epo

Opponent name: BP OIL INTERNATIONAL LTD.

NLR1 Nl: opposition has been filed with the epo

Opponent name: BASF AKTIENGESELLSCHAFT

Opponent name: BP OIL INTERNATIONAL LTD.

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

PLCK Communication despatched that opposition was rejected

Free format text: ORIGINAL CODE: EPIDOSNREJ1

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APAW Appeal reference deleted

Free format text: ORIGINAL CODE: EPIDOSDREFNO

APAY Date of receipt of notice of appeal deleted

Free format text: ORIGINAL CODE: EPIDOSDNOA2O

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APBQ Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3O

APBQ Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3O

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

PLBN Opposition rejected

Free format text: ORIGINAL CODE: 0009273

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: OPPOSITION REJECTED

27O Opposition rejected

Effective date: 20061023

NLR2 Nl: decision of opposition

Effective date: 20061023

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20120323

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20130315

Year of fee payment: 16

Ref country code: GB

Payment date: 20130225

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20130328

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20130312

Year of fee payment: 16

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69807448

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20141001

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20140320

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20141128

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69807448

Country of ref document: DE

Effective date: 20141001

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140320

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141001

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141001

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140320