EP1230327B1 - Additif pour carburant permettant de prevenir la recession des sieges de soupape - Google Patents

Additif pour carburant permettant de prevenir la recession des sieges de soupape Download PDF

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Publication number
EP1230327B1
EP1230327B1 EP00948084A EP00948084A EP1230327B1 EP 1230327 B1 EP1230327 B1 EP 1230327B1 EP 00948084 A EP00948084 A EP 00948084A EP 00948084 A EP00948084 A EP 00948084A EP 1230327 B1 EP1230327 B1 EP 1230327B1
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Prior art keywords
potassium
fuel
iron
ferrocene
composition
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EP00948084A
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German (de)
English (en)
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EP1230327A1 (fr
Inventor
Simon Christopher Mulqueen
Matthew Vincent
Stephen Leonard Cook
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Innospec Ltd
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Associated Octel Co Ltd
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Priority claimed from GBGB9920587.4A external-priority patent/GB9920587D0/en
Priority claimed from GBGB9925983.0A external-priority patent/GB9925983D0/en
Priority claimed from GBGB9925982.2A external-priority patent/GB9925982D0/en
Priority claimed from GBGB9926432.7A external-priority patent/GB9926432D0/en
Priority claimed from GB0011064A external-priority patent/GB2347433B/en
Application filed by Associated Octel Co Ltd filed Critical Associated Octel Co Ltd
Publication of EP1230327A1 publication Critical patent/EP1230327A1/fr
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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
    • 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
    • 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
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • 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
    • C10L1/26—Organic compounds containing phosphorus
    • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
    • C10L1/2658—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) amine salts
    • 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
    • C10L1/30—Organic compounds compounds not mentioned before (complexes)
    • C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)

Definitions

  • the present invention relates to a use.
  • the present invention relates to additives for fuel, fuel compositions containing them and the use thereof.
  • the invention relates to additives effective in preventing a phenomenon well known to those skilled in the art as exhaust valve seat recession (VSR).
  • VSR exhaust valve seat recession
  • Metal or metal containing additives have been incorporated in fuel compositions for many years.
  • the additives may provide a number of effects on the fuel.
  • Certain additives are known to improve the combustion properties of the fuel, for example certain additives may increase the octane number of petroleum fuels.
  • the additives may also provide an effect during combustion, in particular during combustion in an internal combustion engine.
  • metal or metal containing additives may deposit metal or metal compounds on surface of an internal combustion engine during combustion.
  • metal or metal compounds may deposit on the valves or valve seats of an internal combustion engine. Such deposits may protect these components of the engine from wear caused during operation, for example the deposits may protect the valve seats from wear and consequential recession.
  • Barker gives indications of the effect of various metallic fuel additives in preventing VSR in gasoline engines.
  • the metals considered include lead, zinc, iron, sodium and vanadium.
  • Lead at a treat rate of 13.0 mgPb/l was very effective in preventing VSR, followed by zinc, vanadium, sodium and iron. All these latter metals were markedly less effective than lead despite being added at a metal treat rate of 18.5 mgM/l, where M denotes the metal tested.
  • Examinations of wear debris showed that oxides of iron were present on the valve seat, These abrasive materials were implicated in the wear process itself, suggesting that the presence of iron in the gasoline would not necessarily be conducive to protection against VSR.
  • the relatively poor performance of iron as an additive to protect against VSR is consistent with this view.
  • Ferrocene is a well-known metallic fuel additive with a significant capability to increase octane quality in unleaded gasoline. It is used as an octane trimming additive at refineries to enhance octane quality in gasoline, to assist meeting gasoline octane specifications.
  • the performance of this product as an additive to protect against VSR was explored by Barker as discussed above, and found to be relatively poor at a treat rate of 18.5mgFe/litre, which equates to 25mgFe/kg.
  • iron added as ferrocene is used typically at a treat rate of 9mgFe/kg. This treat rate of additive would be expected to provide very limited protection from VSR. This can in fact be shown to be the case.
  • VSR protection from the phosphorus additive Valvemaster lies in the formation of P 2 O 5 in the engine. Deposits are laid down between the exhaust valve and its seat, preventing the metal to metal contact which leads to erosion or recession of the valve seat. The deposition of such protective deposits was postulated as described earlier by Colwell in 1931 and by Barker in 1973.
  • the products of combustion of PLUTOcen® are iron oxides, which are slightly abrasive materials not expected to provide VSR protection.
  • VSR valve seat recession
  • compositions for the prevention and/or inhibition of valve seat recession of an internal combustion engine comprising (i) a potassium compound selected from the group consisting of potassium sulphonates, potassium carboxylates and mixtures thereof; and (ii) a ferrocene and/or a substituted ferrocene.
  • a fuel additive composition comprising (i) a potassium compound selected from the group consisting of potassium sulphonates, potassium carboxylates and mixtures thereof; and (ii) a ferrocene and/or a substituted ferrocene.
  • composition is present in amount to provide the required improvement of the combustion properties and prevention of valve seat recession.
  • VSR is an abbreviation of valve seat recession.
  • valve seat recession of an internal combustion engine, such as a petrol/gasoline internal combustion engine.
  • the iron and/or iron compound may be combined with potassium and/or a potassium compound and unexpected advantages observed.
  • the VSR prevention performance of potassium at a metal treat rate of 8mgK/kg is well established as moderate.
  • the combination of the two metals provides a level of protection from VSR which is surprising and unexpected.
  • the combination of potassium with ferrocene increases the octane quality of the blend to which the combination is added.
  • VSR additives are designed so as to prevent misfueling, which should thus only be capable of occurring where an aftermarket additive is inappropriately used.
  • the additive comprises a combination of iron and phosphorus
  • VSR protection and various other benefits can be obtained with a further reduction even in this small risk, because of the reduced phosphorus content of the combination.
  • the combination additive(s) are believed to function by deposition of high temperature lubricant thin films on and around the valve face and seat. Without being bound by theory it is believed that the mechanism(s) by which the combination additives are successful is/are:
  • the potassium and/or potassium compound is a potassium compound.
  • Potassium salts used may be acidic, neutral or basic (that is over-based, hyperbased or superbased).
  • Acidic salts may be prepared with an excess of organic acid over potassium, neutral salts react essentially stoichiometric quantities of acid and base and basic salts contain an excess of cations, and are typically prepared by 'blowing' a suspension of metal base in a solution of organic acid with gaseous CO 2 .
  • colloidal suspensions of inorganic salts of potassium may be used.
  • Suitable organic acids for use in preparing the potassium compound are extensively reviewed in WO87/01126 to Johnston et al. These include sulphur acids, carboxylic acids and phosphorus acids.
  • the potassium compound is prepared from a sulphur acid.
  • Sulphur acids include sulphonic, sulphamic, thiosulphonic, sulphenic, sulphinic, partial ester sulphuric, sulphurous and thiosulphuric acids.
  • the sulphur acids may be aliphatic or aromatic, including mono- or poly-nuclear aromatic acids or cycloaliphatic compounds. Sulphonates from detergent manufacture by-products are frequently encountered.
  • Carboxylic acids include aliphatic, cycloaliphatic and aromatic mono- and poly-basic carboxylic acids; naphthenic, alkyl or alkenyl cyclopentanoic and hexanoic acids and the corresponding aromatic acids. Branched chain carboxylic acids, including 2-ethylhexanoic acid and propylene tetramer substituted maleic acids may be used. Carboxylic acid fractions featuring various, mixed hydrocarbon chains, such as tall oils and rosins are also encountered.
  • Salts of phenols may be used. These are of the general formula: (R*)a-(Ar*)-(OH)m where R* is an aliphatic group of 4 to 400 C atoms, a is an integer of 1-4, Ar* is a polyvalent aromatic hydrocarbon nucleus of up to about 14 C atoms and m is an integer from 1-4, provided that there are at least about 8 C atoms per acid equivalent provided by the R* groups.
  • the R* groups may be substituted provided that this does not alter the essentially hydrocarbon character of the groups.
  • Phosphorus acids may also be used, for example the phosphonic and thiophosphonic acids prepared by reaction of P 2 S 5 with petroleum fractions such as bright stock or with polymeric materials prepared from C 2 to C 6 mono-olefins, such as poly-(butenes).
  • P 2 S 5 may also be used, for example the phosphonic and thiophosphonic acids prepared by reaction of P 2 S 5 with petroleum fractions such as bright stock or with polymeric materials prepared from C 2 to C 6 mono-olefins, such as poly-(butenes).
  • Appropriate technology for preparation of a range of phosphorus additives is referenced in WO 87/01126.
  • EP 207,560 and EP 555,006 describe ranges of succinic acid derivatives substituted on at least one of the alpha carbon atoms with a C 20 to C 200 hydrocarbyl group, optionally connected to the other alpha-carbon atom by a hydrocarbon moiety of from 1 to 6 carbon atoms.
  • Such derivatives may be further derivatised by reaction of one carboxyl group with an alcohol or an amine preparing, respectively, the hemi-ester or the amide.
  • Preferred acid salts are those of potassium with the succinic acid derivatives, as described immediately above, or of alkyl benzene sulphonic acids, especially dodecyl benzene sulphonic acid, from detergent manufacture.
  • Preferred neutral salts are over based salts. Salts which are resistant to extraction into aqueous phases are preferred.
  • Potassium ions may be employed as a mixture of solution and colloidal suspension sources.
  • the iron and/or iron compound is an iron compound.
  • the iron compound is a ferrocene and/or a substituted ferrocene.
  • the iron compound is an iron complex selected from dicyclopentadienyl and substituted-dicydopentadienyl.
  • the iron compound may be an iron complex of dicyclopentadienyl or substituted-dicyclopentadienyl, wherein the substituents can be, for example, one or more C 1-5 alkyl groups, preferably C 1-2 alkyl groups. A combination of such iron complexes may also be used.
  • Suitable alkyl-substituted-dicyclopentadienyl iron complexes are cyclopentadienyl-(methylcyclopentadienyl) iron, cyclopentadienyl(ethyl-cyclopentadienyl) iron, bis-(methylcyclopentadienyl) iron bis-(ethylcyclopentadienyl) iron, bis-(1,2-dimethylcyclopentadienyl) iron, iron pentacarbonyl, and bis-(1-methyl-3-ethylcyclo-pentadienyl) iron.
  • These iron complexes can be prepared by the processes taught in US-A-2680756, US-A-2804468, GB-A-0733129 and GB-A-0763550.
  • Suitable iron complexes are dicyclopentadienyl iron and/or bis-(methylcyclo-pentadienyl) iron.
  • a highly preferred iron complex is ferrocene (i.e. dicyclopentadienyl iron).
  • Substituted ferrocenes are known and may be used in the present invention (see e.g. Comprehensive Organic Chemistry, Eds. Wilkinson et al., Pergamon 1982, Vol. 4:475-494 and Vol. 8:1014-1043).
  • Substituted ferrocenes for use in the invention include those in which substitution may be on either or both of the cyclopentadienyl groups.
  • Suitable substituents include, for example, one or more C 1-5 alkyl groups, preferably C 1-2 alkyl groups.
  • Particularly suitable alkyl-substituted-dicyclopentadienyl iron complexes include cyclopentadienyl(methylcyclopentadienyl) iron, bis-(methylcyclopentadienyl) iron, bis-(ethylcyclopentadienyl) iron, bis-(1,2-dimethylcyclopentadienyl) iron and 2,2'-diethylferrocenyl-propane.
  • substituents that may be present on the cyclopentadienyl rings include cycloalkyl groups such as cyclopentyl, aryl groups such as tolylphenyl, and acetyl groups, such as present in diacetyl ferrocene.
  • a particularly useful substituent is the hydroxyisopropyl group, resulting in (-hydroxyisopropyl) ferrocene.
  • (-hydroxyisopropyl)ferrocene is a room temperature liquid.
  • organometallic complexes of iron may also be used in the invention, to the extent that these are fuel soluble and stable.
  • Such complexes include, for example, iron pentacarbonyl, di-iron nonacarbonyl, (1,3-butadiene)-iron tricarbonyl, (cyclopentadienyl)-iron dicarbonyl dimer and the diisobutylene complex of iron pentacarbonyl.
  • Salts such as di-tetralin iron tetraphenylborate (Fe(C 10 H 12 ) 2 (B(C 6 H 5 ) 4 ) 2 ) may also be employed.
  • the substituted ferrocenes are particularly preferred iron compounds for use in the invention.
  • Ferrocene itself is an especially preferred iron compound on this basis.
  • Ferrocene of suitable purity is sold in a range of useful forms as PLUTOcen® and as solutions, Satacen®, both by Octel GmbH,
  • the iron compounds for use in the invention need not feature iron-carbon bonds in order to be fuel soluble and stable. Salts may be used; these may be neutral or overbased. Thus, for example, overbased soaps including iron stearate, iron oleate and iron naphthenate may be used. Methods for the preparation of metal soaps are described in The Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed, Vol. 8:432-445, John WiJey & Sons, 1993. Suitable stoichiometric, or neutral, iron carboxylates for use in the invention include the so-called 'drier-iron' species, such as iron tris(2-ethylhexanoate) [19583-54-1].
  • Iron complexes not featuring metal-carbon bonds and not prepared using carbonation may also be used in the invention provided these are adequately fuel soluble and stable.
  • Examples include complexes with -diketonates, such as tetramethylheptanedionate.
  • Iron complexes of the following chelating ligands are also suitable for use in the invention:
  • Suitable iron picrates for use in the invention include those described in US-A-4,370,147 and US-A-4,265,639.
  • iron-containing compounds for use in the invention include those of the formula M(R)x.nL wherein; M is an iron cation; R is the residue of an organic compound RH in which R is an organic group containing an active hydrogen atom H replaceable by the metal M and attached to an O, S, P, N or C atom in the group R; x is 2 or 3; n is 0 or a positive integer indicating the number of donor ligand molecules forming a dative bond with the metal cation; and L is a species capable of acting as a Lewis base.
  • a fuel composition comprising (i) a potassium compound selected from the group consisting of potassium sulphonates, potassium carboxylates and mixtures thereof; (ii) a ferrocene and/or a substituted ferrocene; and (iii) a fuel.
  • the term 'fuel' covers compositions containing a major amount of gasoline base fuel suitable for use in spark-ignition engines.
  • These base fuels may comprise mixtures of saturated, olefinic and aromatic hydrocarbons. They can be derived from straight-run gasoline, synthetically produced aromatic hydrocarbon mixtures, thermally or catalytically cracked hydrocarbon feedstocks, hydrocracked petroleum fractions or catalytically reformed hydrocarbons.
  • Motor gasolines are defined by ASTM D-439-73, aviation gasolines typically have a narrower boiling range of 37 to 165°C.
  • the gasoline may also contain various blending components designed to provide octane number, such as MTBE, TAME or ETBE as non-limiting examples.
  • a proportion of the hydrocarbons may also be replaced for example by alcohols, ethers (as above), esters or ketones.
  • the octane number of the gasoline will be greater than 65.
  • the iron compound provides elemental iron in an amount of at least 5 mg per kg of fuel. More preferably the iron compound provides elemental iron in an amount of at least 30 mg per kg of fuel or in an amount of from 7 to 10 mg per kg of fuel.
  • the fuel is gasoline.
  • the fuel may further comprise performance-enhancing additives.
  • performance-enhancing additives include corrosion inhibitors, rust inhibitors, gum inhibitors, anti-oxidants, solvent oils, anti-static agents, dyes, anti-icing agents, ashless dispersants and detergents.
  • the fuel additives according to the invention may be added as part of a package to the fuel prior to combustion. This may be done at any stage in the fuel supply chain (for example, at the refinery or distribution terminal) or may be added via a dosing device on-board the vehicle, either to the fuel or even separately direct into the combustion chamber or inlet system.
  • the fuel additives may be added to the fuel in the vehicle fuel tank by the user, a so-called 'aftermarket' treatment.
  • the invention further comprises an additive solution for addition to a fuel.
  • an additive might be dosed at any stage in the fuel supply chain prior to combustion of the fuel.
  • the fuel additives of the invention may be dosed to the fuel at any stage in the fuel supply chain.
  • each additive is added to the fuel close to the engine or combustion systems, within the fuel storage system for the engine at the refinery, distribution terminal or at any other stage in the fuel supply chain, including aftermarket use.
  • the additive may be added to the fuel at the refinery or at the distribution terminal.
  • the iron and potassium components may be added together or separately, providing an additional valuable flexibility in use. If added together, they will be dissolved in the minimum amount of fuel compatible solvent commensurate with the need to provide a pumpable solution and avoid crystallisation/separation of any of the components at low temperatures, e.g. about -30°C.
  • the iron material such as PLUTOcen® is added at the refinery as a blending component for octane trimming, to meet the required product octane specification, thus fulfilling the well known and valuable role to the refiner of an octane enhancing agent.
  • the potassium component can be added to the finished fuel at the distribution terminal, in order to produce a product known to those in the Industry as a "lead replacement gasoline” (LRG) or "lead replacement petrol” (LRP).
  • the volume of solvent used will be such as to provide a non-viscous solution, suitable for use in a dispenser bottle or syringe pack.
  • concentration of iron and potassium will be such that some convenient and easily recalled treat rate (e.g. about 1 cm 3 per litre of fuel) is required.
  • the solvents to be used should be readily fuel soluble and compatible, including with respect to boiling point range, and preferably will have flash points in excess of 62°C for ease of storage.
  • the additive solution may optionally contain additional components beyond the iron and potassium compounds- These components include corrosion inhibitors, rust inhibitors, gum inhibitors, anti-oxidants, solvent oils, anti-static agents, dyes, anti-icing agents, ashless dispersants and detergents as a non-limiting list. Where any additional component is employed, the use of detergents, especially poly-(butenyl)succinimide based detergents, is preferred.
  • the test protocol utilised a 1.3 litre 4 cylinder engine having a cast iron cylinder head without valve seat inserts.
  • the engine was operated for a total of 70 hours comprising 50 hours at 3,800 rev/min and 23 kW load, and 20 hours at 5,500 rev/min and 42 kW load. In practice, this condition constituted wide open throttle (WOT) operation.
  • WOT wide open throttle
  • test car is operated according to the cycle shown below. Valve stem to rocker-pad clearances are checked every 4 hours during the actual test. Overall test duration is 100 cycles, but tests are terminated early when significant valve recession is observed. Overall wear and hourly wear rates for the additised fuels are compared to those from gasoline containing 0.03 to 0.15 g/l of lead as tetra-ethyl lead. Tests using non-additised unleaded gasoline are of somewhat short duration, Time, min Speed, km/h rpm Cumulative distance, km 5 80 3000 6.67 20 100 3750 40.0 10 120 4500 60.0 10 80 3000 73.33 20 100 3750 106.67 Overall duration 65 minutes. Overall average speed 98.5 km/h
  • the performance of the combination of additives is superior to that which would be expected by comparing the performance of the individual components at or around the dose rates used. That is, indications of a synergistic effect are observed.
  • This document defines a test procedure for evaluating claims made for devices, and fuel additives, to enable a spark ignition engine designed for leaded petrol to operate continuously on unleaded petrol.
  • the objective of the test procedure is to quantify and to measure exhaust valve seat recession experienced with any device or fuel additive assessed. From measurements recorded, an assessment of the engine protection provided by candidate devices or fuel additives, and their potential suitability to prevent valve seat recession with continuous use of unleaded petrol, can be made.
  • test engine shall have the following specification: Type Rover "A" series Capacity, cc 1275 No of cylinders 4 Valve operation OHV Bore, mm 70.6 Stroke, mm 81.3 Compression ratio 9.75:1 Fuel system Carburettor Type SU HIF 44
  • the engine shall be inspected prior to its use in testing to ensure that the cylinder head fitted
  • the engine shall be rebuilt prior to its use in testing with the following new components:
  • All valves shall be ground in to ensure removal of lead deposits from valve seats, from previous operation on leaded petrol.
  • the engine shall be operated over a range of speed and load conditions to ensure normal operation. Ignition advance and exhaust CO level shall be checked and set to manufacturer's specification. As a final check, a full load power curve shall be carried out.
  • Valve tip location shall be measured using a jig in combination with a micrometer depth gauge. See Figure 1.
  • the distance "a” is defined as the valve stand down height.
  • Valve stand down heights shall be measured as follows, and measurements recorded:
  • valve seat recession test shall be run in two stages, as follows:
  • valve tip location measurements prior to the start of test are given in Section 5.
  • the same technique is used to measure valve seat recession at intervals during the test.
  • the valve stand down height, after 30 minutes cooling, shall be measured and recorded at the following intervals: Stage 1: every 10 hours and at the end of 50 hours Stage 2: every 5 hours and at the end of 20 hours
  • valve clearances shall be checked and adjusted to manufacturer's specification.
  • the test fuel shall be taken from a batch of unleaded petrol of adequate size to enable all candidate devices or fuel additives to be tested using the same type of fuel. Where a device is to be tested, no other additive shall be added to the fuel unless the additive comprises an integral part of the device. Where a fuel additive is to be tested, it shall be added to the test fuel prior to commencing the test, using the mixing procedure defined in the Appendix A.
  • test engine shall be dismantled (cylinder head removed) and prepared according to the requirements of Section 5, in preparation for the test on each candidate device or fuel additive.
  • Crankcase lubricating oil shall be drained and refilled as part of the preparation for each test.
  • bottom end shall be inspected at least every 4th test to ensure satisfactory mechanical condition e.g. blow by, piston slap, between tests.
  • Replacement pistons shall be fitted, and bores honed to maintain the engine in a satisfactory operating condition.
  • test fuel containing 0.03g Pb/l shall be employed for a further test to assess relative valve seat recession performance.
  • This test fuel shall be produced by adding the required amount of lead alkyl additive to the unleaded test fuel employed for the previous tests.
  • Valve 1 (exh) Valve 2 (inl) Valve 3 (inl) Valve 4 (exh) Valve 5 (exh) Valve 6 (inl) Valve 7 (inl) Valve 8 (exh) Valve Cylinder head
  • the base fuel for the test shall be unleaded petrol meeting the requirements of Sections 3.5 and 8.
  • a sample of fuel shall be routinely taken from each of the barrels used for the test.
  • the samples can be sent for analysis if required.

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  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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Claims (12)

  1. Utilisation d'une composition permettant de prévenir et/ou d'entraver le retrait des sièges de soupape d'un moteur à combustion interne, la composition comprenant
    (i) un composé de potassium choisi dans le groupe constitué de sulfonates de potassium, de carboxylates de potassium et de mélanges de ceux-ci ; et
    (ii) un ferrocène et/ou un ferrocène substitué.
  2. Composition d'additif pour carburant comprenant
    (i) un composé de potassium choisi dans le groupe constitué de sulfonates de potassium, de carboxylates de potassium et de mélanges de ceux-ci ; et
    (ii) un ferrocène et/ou un ferrocène substitué.
  3. Composition de carburant comprenant
    (i) un composé de potassium choisi dans le groupe constitué de sulfonates de potassium, de carboxylates de potassium et de mélanges de ceux-ci ;
    (ii) un ferrocène et/ou un ferrocène substitué ; et
    (iii) un carburant.
  4. Utilisation ou composition selon l'une quelconque des revendications précédentes, dans laquelle le composé de potassium comprend un sulfonate de potassium.
  5. Utilisation ou composition selon la revendication 4, dans laquelle le sulfonate de potassium est un sel acide de potassium avec un acide alkylbenzènesulfonique.
  6. Utilisation ou composition selon la revendication 5, dans laquelle le sulfonate de potassium est un sel acide de potassium avec de l'acide dodécylbenzènesulfonique.
  7. Utilisation ou composition selon l'une quelconque des revendications précédentes, dans laquelle le composé de potassium comprend un carboxylate de potassium.
  8. Utilisation ou composition selon la revendication 7, dans laquelle le carboxylate de potassium est un sel acide de potassium avec un dérivé d'acide succinique.
  9. Utilisation ou composition selon l'une quelconque des revendications précédentes, dans laquelle le ferrocène et/ou ferrocène substitué est un complexe de fer choisi entre un complexe de dicyclopentadiényle et un complexe de dicyclopentadiényle substitué.
  10. Utilisation ou composition selon l'une quelconque des revendications précédentes, dans laquelle le ferrocène et/ou le ferrocène substitué fournissent du fer élémentaire en une quantité d'au moins 5 mg par kg de carburant.
  11. Utilisation ou composition selon l'une quelconque des revendications précédentes, dans laquelle le ferrocène et/ou le ferrocène substitué fournissent du fer élémentaire en une quantité d'au moins 30 mg par kg de carburant.
  12. Utilisation ou composition selon l'une quelconque des revendications 1 à 10, dans laquelle le ferrocène et/ou le ferrocène substitué fournissent du fer élémentaire en une quantité de 7 à 10 mg par kg de carburant.
EP00948084A 1999-09-01 2000-07-07 Additif pour carburant permettant de prevenir la recession des sieges de soupape Expired - Lifetime EP1230327B1 (fr)

Applications Claiming Priority (11)

Application Number Priority Date Filing Date Title
GBGB9920587.4A GB9920587D0 (en) 1999-09-01 1999-09-01 Composition
GB9920587 1999-09-01
GBGB9925983.0A GB9925983D0 (en) 1999-11-02 1999-11-02 Fuel additives
GBGB9925982.2A GB9925982D0 (en) 1999-11-02 1999-11-02 Fuel additives
GB9925982 1999-11-02
GB9925983 1999-11-02
GBGB9926432.7A GB9926432D0 (en) 1999-11-08 1999-11-08 Composition
GB9926432 1999-11-08
GB0011064 2000-05-08
GB0011064A GB2347433B (en) 1999-09-01 2000-05-08 Compsition
PCT/GB2000/002626 WO2001016257A1 (fr) 1999-09-01 2000-07-07 Additif pour carburant permettant de prevenir la recession des sieges de soupape

Publications (2)

Publication Number Publication Date
EP1230327A1 EP1230327A1 (fr) 2002-08-14
EP1230327B1 true EP1230327B1 (fr) 2006-06-07

Family

ID=27515944

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00948084A Expired - Lifetime EP1230327B1 (fr) 1999-09-01 2000-07-07 Additif pour carburant permettant de prevenir la recession des sieges de soupape

Country Status (5)

Country Link
EP (1) EP1230327B1 (fr)
AT (1) ATE328986T1 (fr)
AU (1) AU773552B2 (fr)
DE (1) DE60028599T2 (fr)
WO (1) WO2001016257A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8177865B2 (en) 2009-03-18 2012-05-15 Shell Oil Company High power diesel fuel compositions comprising metal carboxylate and method for increasing maximum power output of diesel engines using metal carboxylate
US8950366B2 (en) 2013-05-07 2015-02-10 Ford Global Technologies, Llc Method for reducing valve recession in gaseous fuel engines
US9453465B2 (en) 2013-05-07 2016-09-27 Ford Global Technologies, Llc Direct injection of diluents or secondary fuels in gaseous fuel engines
US9624872B2 (en) 2013-05-07 2017-04-18 Ford Global Technologies, Llc Method for reducing valve recession in gaseous fuel engines
US9777646B2 (en) 2013-05-07 2017-10-03 Ford Global Technologies, Llc Direct injection of diluents or secondary fuels in gaseous fuel engines
US9909514B2 (en) 2013-05-07 2018-03-06 Ford Global Technologies, Llc Direct injection of diluents or secondary fuels in gaseous fuel engines

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Publication number Priority date Publication date Assignee Title
GB0229442D0 (en) * 2002-12-18 2003-01-22 Ass Octel Use
WO2005087901A2 (fr) * 2004-03-09 2005-09-22 Innospec Limited Composition
RO127197A1 (ro) 2010-02-10 2012-03-30 Marine Resources Exploration International B.V. Compoziţii sinergice de aditivi antidetonanţi pentru benzine

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BE552837A (fr) *
GB737092A (en) * 1952-11-10 1955-09-21 Shell Refining & Marketing Co Fuels and lubricants for internal combustion engines
GB835870A (en) * 1958-01-15 1960-05-25 Exxon Research Engineering Co Fuel compositions
US3674450A (en) * 1971-04-23 1972-07-04 Cities Service Oil Co Antistatic additive for hydrocarbon fuels
US4370147A (en) * 1979-10-01 1983-01-25 Horizon Chemical, Inc. Fuel for compression ignition engines
GB2106134B (en) * 1981-07-22 1984-11-21 Farsan Ltd Stabilizers for oil-water mixtures
AT373274B (de) * 1981-10-12 1984-01-10 Lang Chem Tech Prod Zusatz mit verbrennungsfoerdernder und russhemmender wirkung zu heizoelen, dieselkraftstoffen und sonstigen fluessigen brenn- und treibstoffen, sowie fluessige brennund treibstoffe mit diesem zusatz
US4720288A (en) * 1986-03-27 1988-01-19 Union Oil Company Of California Gasoline fuel composition
EP0288296B2 (fr) * 1987-04-23 1999-03-31 Lubrizol Adibis Holdings (Uk) Limited Composition de combustible contenant un additif pour diminuer le recul de l'assise de soupape
GB2248068A (en) * 1990-09-21 1992-03-25 Exxon Chemical Patents Inc Oil compositions and novel additives
AU668151B2 (en) * 1992-05-06 1996-04-26 Afton Chemical Corporation Composition for control of induction system deposits

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8177865B2 (en) 2009-03-18 2012-05-15 Shell Oil Company High power diesel fuel compositions comprising metal carboxylate and method for increasing maximum power output of diesel engines using metal carboxylate
US8950366B2 (en) 2013-05-07 2015-02-10 Ford Global Technologies, Llc Method for reducing valve recession in gaseous fuel engines
US9453465B2 (en) 2013-05-07 2016-09-27 Ford Global Technologies, Llc Direct injection of diluents or secondary fuels in gaseous fuel engines
US9624872B2 (en) 2013-05-07 2017-04-18 Ford Global Technologies, Llc Method for reducing valve recession in gaseous fuel engines
US9777646B2 (en) 2013-05-07 2017-10-03 Ford Global Technologies, Llc Direct injection of diluents or secondary fuels in gaseous fuel engines
US9909514B2 (en) 2013-05-07 2018-03-06 Ford Global Technologies, Llc Direct injection of diluents or secondary fuels in gaseous fuel engines

Also Published As

Publication number Publication date
WO2001016257A1 (fr) 2001-03-08
DE60028599T2 (de) 2007-05-16
EP1230327A1 (fr) 2002-08-14
ATE328986T1 (de) 2006-06-15
DE60028599D1 (de) 2006-07-20
AU6165900A (en) 2001-03-26
AU773552B2 (en) 2004-05-27

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