WO2000011119A1 - Additifs pour carburants - Google Patents

Additifs pour carburants Download PDF

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Publication number
WO2000011119A1
WO2000011119A1 PCT/GB1999/002751 GB9902751W WO0011119A1 WO 2000011119 A1 WO2000011119 A1 WO 2000011119A1 GB 9902751 W GB9902751 W GB 9902751W WO 0011119 A1 WO0011119 A1 WO 0011119A1
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Prior art keywords
formula
compound
metal
fuel
group
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PCT/GB1999/002751
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English (en)
Inventor
Stephen Leonard Cook
Jacqueline Glen Reid
Paul Joseph Richards
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The Associated Octel Company Limited
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Priority to AU54363/99A priority Critical patent/AU5436399A/en
Priority to EP99940373A priority patent/EP1112339A1/fr
Publication of WO2000011119A1 publication Critical patent/WO2000011119A1/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
    • 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
    • C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/593—Dicarboxylic acid esters having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/602—Dicarboxylic acid esters having at least two carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
    • 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
    • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal

Definitions

  • the present invention relates to additives for liquid hydrocarbon fuels, and fuel compositions containing them. More specifically the invention relates to additives effective to reduce the particulate and/or unburnt hydrocarbon content of exhaust gas emissions from distillate hydrocarbon fuels such as diesel and heating oils.
  • Diesel fuels and diesel engines are particularly prone to the emission of small size particulate material in the exhaust gas. These particulates include not only those which are visible as smoke emission, and to which diesel engines are prone especially when the engine is overloaded, worn or badly maintained, but also those which are normally invisible to the naked eye. Particulate emission by diesel engines is a major source of atmospheric pollution. Similar problems can also arise during the combustion of other distillate fuel oils, e.g. heating oils.
  • Succinic acid derivatives in particular those derived from poly (butenyl) succinic anhydride, are known to be useful as metal carriers in fuel additive compositions. Their metal salts or complexes with alkali and alkaline earth metals are particularly effective in particulates suppression and in the regeneration of diesel particulate filters, as outlined in O-A-96/34074 and O-A-96/34075. Whilst in many respects excellent, these poly (butenyl) succinate carriers exhibit the following limitations:
  • R 1 is an optionally substituted, saturated or unsaturated, straight-chained or branched hydrocarbyl group, preferably containing from 6 to 40 carbon atoms, more preferably 8 to 24 carbon atoms, e.g. 12 to 24 carbon atoms;
  • R 2 and R 3 represents a hydrogen atom and the remaining one of R 2 and R 3 represents a straight-chained or branched alkyl group, preferably a Cj_ 10 alkyl, e.g. a Cj_ 6 alkyl group;
  • R 4 represents a hydrogen atom or a straight-chained or branched alkyl group, preferably a Cj.g alkyl, e.g. a Cj . _ 4 alkyl group;
  • R 1 and R 4 may be linked together to form an optionally substituted, saturated or unsaturated, 5- or 6-membered, preferably 6-membered, carbocyclic ring) and metal salts and complexes, optical isomers and diastereoisomers thereof .
  • R 1 is preferably an alkenyl or poly (alkenyl) group, preferably a
  • R 1 is a poly(C 2 _ 4 alkenyl) group, for example a poly (propenyl) , poly (butenyl) , poly (isobutenyl) , or tetrapropenyl group.
  • suitable R 1 groups include 2-octenyl, 2-dodecenyl or 2-octadecenyl . These R 1 groups may optionally be hydrogenated to remove the unsaturation.
  • other suitable R 1 groups include saturated alkyl groups, preferably C 6 _ 40 alkyl, more preferably C 8 _ 24 alkyl, e.g. C 12 _ 24 alkyl.
  • substituents may be present in the compounds of the invention, in particular in group R 1 .
  • Typical substituents include alkyl groups, for example C ⁇ _ 6 alkyl groups, more preferably Cj_ 4 alkyl groups, optionally substituted by hydroxy, alkoxy, cyano, nitrile or halogen groups.
  • Examples of particular substituents include methyl, ethyl, isopropyl, n-propyl, t-butyl and -butyl .
  • R 1 is a poly (alkenyl) group, in particular a poly(C 2 . 6 alkenyl) group, e.g. poly (butenyl)
  • R 1 may be substituted with one or more additional groups of the formula:
  • R 2 and R 3 when not hydrogen are preferably sterically hindered alkyl groups, typically secondary alkyl groups.
  • Suitable alkyl groups include isopropyl, secondary butyl and
  • R 2 or R 3 is an isopropyl group
  • R 4 is a hydrogen atom.
  • poly(alkene) and poly (alkenyl) are intended to cover products derived from the polymerisation of an olefin or mixture of olefins, in particular ⁇ -olefins, preferably C 2 _ 10 ⁇ -olefins, especially butenes .
  • Such compounds will comprise at least one olefinic bond, typically at least one vinylidene group.
  • Particularly preferred for use in the invention are those compounds of formula I in which R 1 is derived from the polymerisation of butenes, i.e.
  • R 1 is poly (butenyl) .
  • poly (butenyl) is intended to cover both oligomers and polymers prepared from isobutene and those from mixed C 4 olefin streams, i.e. comprising isobutene, but-1-ene and cis and trans but-2-ene.
  • the metal carriers formed from the hemi-esters of compounds of formula I may be regarded as salts. Without wishing to be bound by theory, however, it is believed that the ester groups co-ordinate, whether inter- or intra-molecularly, to the metal ions. They may thus fairly be referred to as metal complexes.
  • Preferred metal salts or complexes formed from the hemi- esters of formula I include those of formula II:
  • R 2 and R 3 is an alkali or alkaline earth metal M of valency n, and the remaining one of R 2 and R 3 is a straight-chained or branched alkyl group, preferably a Ci_ 10 alkyl, e.g. a C ⁇ 6 alkyl group;
  • M is selected from the group consisting of Na, K, Mg, Ca and Sr. Most preferably, M is K or Sr.
  • the compounds of the invention may be prepared by conventional synthetic techniques, conveniently starting from succinic anhydride or succinic acid derivatives and alcohols, preferably sterically hindered alcohols.
  • the invention also provides a process for the preparation of compounds of formula I, said process comprising at least one of the following steps:
  • R is a straight-chained or branched alkyl group, preferably a C ! _ 10 alkyl, e.g. a C ⁇ alkyl group
  • R 1 and R 4 fined a succinic anhydride derivative of formula IV: wherein R 1 and R 4 fined
  • step (b) reacting a compound of formula III as defined in step (a) together with a succinic acid derivative of formula V:
  • the products of the above reactions may be either single compounds or mixtures of discrete compounds . Typically these will comprise mixtures of compounds of formula I .
  • the starting compounds used in the reactions described above are either known from the literature or can be prepared using conventional synthetic techniques.
  • the reactants may be substituted with functional groups which are inert under the reaction conditions employed, as would be understood by one skilled in the art.
  • any reactive groups present may optionally be protected during the reaction by means of conventional protecting groups which are cleaved again after the reaction. Subsequent cleaving of any protecting group used may be carried out by methods known in the art, for example hydrolysis.
  • the final step in the synthesis of compounds of formula I will thus be deprotection of a protected derivative of a compound of formula I and such a process forms a further aspect of the invention.
  • Preferred compounds of formula III for use in step (a) or step (b) include sterically hindered alcohols, more preferably sterically hindered secondary alcohols.
  • Preferred examples of sterically hindered secondary alcohols include secondary butyl alcohol and 2- ethylhexyl alcohol .
  • An even more preferred example is isopropyl alcohol .
  • Preferred reaction conditions for steps (a) and (b) include ensuring that the alcohol is present in excess over either the cyclic succinic anhydride derivative of formula IV (in step (a) ) or the succinic acid derivative of formula V (in step (b) ) . Reaction in step (a) is performed with no catalyst present. Once all the succinic anhydride or succinic acid derivative has been consumed (followed by FTIR analysis) , the excess alcohol is stripped off to leave the product .
  • suitable poly (butenes) include those distributed by Amoco as ⁇ IndopolTM', by BASF as 'GlissopalTM' and by BP as 'UltravisTM' and 'NapvisTM' .
  • Typical number average molecular weights of commercially available fractions are of 500 amu and upwards. This limits the maximum possible metal content of a PIBSA-derived material prepared from them.
  • Lower molecular weight fractions, such as ' Indopol L-10TM', ' Indopol L-6TM' and 'Napvis X- 10TM' are available and are preferred for use in the invention.
  • ⁇ -olefins Low molecular weight propylene and ethylene oligomers, such as ⁇ -olefins are readily available. Maleinisation can be performed on ⁇ -olefins and fractions to produce 2 -alkenyl succinic anhydrides or on isomerised ⁇ -olefins or fractions resulting in ⁇ -branched 2-alkenyl succinic anhydrides.
  • ASA alkenyl succinic anhydrides
  • Biodegradation in the environment is frequently a requirement for synthetic chemicals in the modern marketplace.
  • the option to use ASA- as opposed to PIBSA-derived materials is an advantage in the preparation of the metal carriers in accordance with the invention.
  • ASAs alkenyl succinic anhydrides
  • the compounds for use in preparing the compounds of the invention will comprise a mixture of compounds of formula IV or V having different R 1 groups resulting from the maleinisation of isomerised ⁇ -olefins or isomerised ⁇ -olefin fractions.
  • the compound of formula IV may conveniently be prepared by reaction of maleic anhydride or an ⁇ -substituted maleic anhydride with an olefin or polyolefin, preferably a monoolefin or diolefin, e.g. a monoolefin such as poly (butene) .
  • the olefin e.g.
  • R 1 is a poly(C 2 _ 6 alkenyl) group
  • a proportion of the R 1 groups may have linked thereto one or more additional succinate groups, essential corresponding to the compounds of formula I .
  • the ratio of succinate groups linked to group R 1 to succinated poly (alkenyl) moieties is preferably from 1:1 to 1.3:1, more preferably from 1.05:1 to 1.15:1.
  • the unsaturation remaining in R 1 following the '2-centre ene' or Diels Alder reactions may be removed by hydrogenation using techniques well-known in the art.
  • the metal salts of the compounds of formula I may be obtained by reacting a source of the metal M, e.g. the elemental metal, a metal alkyl or hydride, an oxide or hydroxide, with a compound of formula I in a hydrocarbon, preferably an aromatic hydrocarbon solvent such as 'ShellSol ABTM ' .
  • a source of the metal M e.g. the elemental metal, a metal alkyl or hydride, an oxide or hydroxide
  • a compound of formula I in a hydrocarbon, preferably an aromatic hydrocarbon solvent such as 'ShellSol ABTM ' .
  • the most convenient source of the metal M will usually be the hydroxide or oxide, preferably the hydroxide .
  • the compounds of the invention may be present in the form of enantiomers or racemates thereof or in the form of their pairs of diastereoisomers .
  • the compounds of formula I may be separated into their diastereoisomers on the basis of their physical/chemical differences by methods known in the art, e.g. by chromatography and/or fractional crystallisation.
  • the compounds of formula I may be resolved into their optical isomers.
  • those compounds having at least one optically active carbon atom may be resolved into their enantiomers, e.g. by chiral chromatography.
  • the compounds of the invention are particularly effective as particulate suppressants in liquid hydrocarbon fuels. It has also been found that the compounds of the invention lead to a reduction in unburnt hydrocarbon emission, not only in the exhaust gas emissions from diesel fuels but from other liquid hydrocarbons as well.
  • the additives also serve to remove preformed soot or carbon deposits in internal combustion engines and fuel injectors of all kinds, including exhaust systems used therewith.
  • the additives of the invention have added value as exhaust emission control agents for reducing unburnt hydrocarbon emissions from liquid hydrocarbon fuels, and as clean-up agents for the removal of soot and carbon deposits resulting from the incomplete combustion of liquid hydrocarbon fuels .
  • the invention provides a fuel additive for liquid hydrocarbon fuels, in particular diesel fuels, comprising at least one metal complex of a compound of formula I, preferably a compound of formula II as hereinbefore defined.
  • the fuel additives in accordance with the invention may additionally comprise an organic, fuel soluble solvent, preferably a hydrocarbon, miscible in all proportions with the fuel.
  • Suitable solvents for this purpose include: aromatic kerosene hydrocarbon solvents such as 'ShellSol ABTM ' (boiling range 186°C to 210°C) , 'ShellSol RTM ' (boiling range 205°C to 270°C) , 'Solvesso 150TM' (boiling range 182°C to 203°C), toluene, xylene, or alcohol mixtures such as 'AcropolTM' (boiling range 216°C to 251°C) .
  • aromatic kerosene hydrocarbon solvents such as 'ShellSol ABTM ' (boiling range 186°C to 210°C) , 'ShellSol RTM ' (boiling range 205°C to 270°C) , 'Solvesso 150TM' (boiling range 182°C to 203°C), toluene, xylene, or alcohol
  • the invention thus provides a fuel additive for liquid hydrocarbon fuels, in particular for diesel fuels, comprising an organic, fuel soluble solvent, preferably a hydrocarbon, miscible in all proportions with the fuel, and at least one metal complex of a compound of formula I as hereinbefore defined.
  • the amount of metal in the additive represents the best compromise between high concentration and the need to achieve low viscosity, as will be readily understood by those skilled in the art.
  • Metal concentrations in the additive may range from 1 to 10% or more by weight, preferably 4 to 6% by weight, for example 5% by weight.
  • the invention thus provides a method of reducing particulate or visible smoke emissions and/or unburned hydrocarbons resulting from the incomplete combustion of liquid hydrocarbon fuels, in particular from diesel fuels, said method comprising the step of incorporating into the fuel prior to combustion an effective amount of a metal complex of a compound of formula I .
  • a metal complex of a compound of formula I as a black smoke, particulate and/or unburned hydrocarbon-reducing additive.
  • the additives in accordance with the invention may be dosed to the fuel at any stage in the fuel supply chain.
  • the additives are added to the fuel close to the engine or combustion systems, within the fuel storage system for the engine or combustor, at the refinery, distribution terminal or at any other stage in the fuel supply chain.
  • the term "fuel” includes any hydrocarbon that can be used to generate power or heat.
  • the term also covers fuel containing other additives such as dyes, cetane improvers, rust inhibitors, antistatic agents, gum inhibitors, metal deactivators, de- emulsifiers, upper cylinder lubricants, antifoam compositions and anti-icing agents.
  • the term covers diesel fuel .
  • diesel fuel means a distillate hydrocarbon fuel for compression ignition internal combustion engines meeting the standards set by BS 2869 Parts 1 and 2 as well as fuels in which hydrocarbons constitute a major component and alternative fuels such as rape seed oil and rape oil methyl ester.
  • Combustion of the fuel can occur in, for example, an engine such as a diesel engine, or any other suitable combustion system.
  • suitable combustion systems include recirculation engine systems, domestic burners and industrial burners.
  • the additive composition of the invention is fuel-soluble or fuel miscible.
  • a preferred composition of the invention is one which can be supplied in concentrated form in a suitable solvent which is fully compatible with diesel and other hydrocarbon fuels, such that blending of fuel and additive may be more easily and readily carried out .
  • the additives in accordance with the invention may be used in combination with a particulate filter enabling collected material to be more readily oxidised.
  • a particulate filter enabling collected material to be more readily oxidised.
  • Many types of filter are known to those skilled in the art including "wall flow” or “cracked wall”, “deep bed” ceramic types and sintered metal types.
  • the additives are suitable for use with all particulate filters, examples of preferred filters include the • Corning EX80TM', the 'NoTox' SiC types (both ceramic wall -flow filters), one constructed from ' 3M NextelTM' fibre (a deep bed type) or an SHW sintered metal DPF.
  • the present invention provides the use of a metal complex of a compound of formula I as a part of an additive composition for the regeneration of particulate filters, particularly diesel particulate filters.
  • the additives in accordance with the invention are capable of providing frequent spontaneous regenerations across a wide range of engine operating conditions using a wide range of fuels, including fuels with realistic sulphur concentration, and at low levels of loading of particulate material within the filter. This results in minimum average pressure drop across the filter, representing minimum fuel efficiency penalty.
  • Regeneration with less carbon in the filter also results in lower thermal stresses arising from the exothermic regeneration.
  • the additives of the invention require minimum adjustment to engine operating parameters (e.g. injection timing) and/or minimum energy input to produce a 'forced' regeneration, whether operating within or outside an envelope wherein spontaneous regenerations are likely to be encountered. These specifications can be achieved at a dose level which provides minimum inorganic ash.
  • the key advantages of the present invention are that it provides additives for diesel fuels that are cost- effective and which provide an overall emissions benefit to the environment on combustion by improving the combustion process and therefore reducing black smoke, particulate and/or unburned hydrocarbon emissions.
  • the additives are of lower viscosity than those of the art and do not interact with antifoams present in diesel fuel.
  • the compounds and additives of this invention may be used in diesel fuels together with other materials used as additives to improve various aspects of fuel or engine performance.
  • these additives would include: detergents, carrier oils, anti-oxidants, corrosion inhibitors, colour stabilisers, metal deactivators, cetane number improvers, other combustion improvers, antifoams, pour point depressants, cold filter plugging point depressants, wax anti-settling additives, dispersants, reodorants, dyes, smoke suppressants, particulate filter regeneration additives and lubricity agents.
  • a further aspect of the present invention provides the use of a metal complex of a compound of formula I as part of a formulation further comprising any of the additives mentioned in the non-limiting list above for use in any of the applications hereinbefore described.
  • Octenyl succinic anhydride (Aldrich, 202.52 g, 0.963 mol) and propan-2-ol (135.5 g, 2.258 mol) were charged to a one litre jacketed SoverelTM reactor fitted with overhead stirrer and reflux condenser. The heating oil supplied to the jacket was warmed to 90°C and the solution stirred and heated for 3 hours.
  • FTIR analysis (ATR device) indicated complete conversion of anhydride to a mixture of ester and carboxylic acid. The mixture was stirred overnight with the oil at 70°C before stripping unreacted propan-2-ol at the rotary evaporator to constant weight of involatiles. Titration against lithium methoxide for residual acidity gave an acid content of 3.81 mmol H + /g.
  • Theoretical value for starting material and hemi-ester product are, respectively, 4.75 and 3.70 mmol H + /g.
  • Tetrapropenyl succinic anhydride (Pentagon, 582.82 g, 2.187 mol) and propan-2-ol (282.37 g, 4.706 mol) were allowed to react as described above, overnight, at an oil temperature of 85°C.
  • FTIR showed complete consumption of the starting anhydride.
  • Acid value of the stripped material was 3.15 mmol H + /g, versus 3.52 for the diacid and 3.06 theoretical for hemi-ester.
  • PentasizeTM 68F (269.73 g) , an alkenyl succinic anhydride prepared from an isomerised mixture of C16 and C18 ⁇ -olefins and having an acid content equivalent to 336.9 mg KOH/g, was reacted with propan-2- ol (64.65 g, 1.078 mol) in the SoverelTM apparatus at 90°C over 16 hours.
  • FTIR ATR showed the reaction to be complete and excess propanol was removed under vacuum.
  • the product had an acid value of 2.48 mmol/g, versus 2.54 theoretical.
  • ShellsolTM (214.43 g) .
  • the two were stirred and warmed to 80°C, forming a homogenous solution.
  • KOH flake 29.83 g, 0.478 mol was added resulting in an exotherm to 106 °C within about 15 minutes. A colour change from colourless to orange-brown was noted.
  • the resulting solution had an acid value of 0.1 mmol/g.
  • Example 2 (106.66 g, 0.333 mol H + ) and ShellsolTM (214.80 g) .
  • the two were stirred and warmed to 76 °C, forming a homogenous solution.
  • KOH flake (12.35 g, 198 mmol) was added, causing an exotherm to 85°C, the solution cooling back to 77°C within 35 minutes, accompanied by dissolution of the solids.
  • KOH (8.03 g, 129 mmol) was added, dissolving within 40 minutes to yield a clear, bright solution.
  • FTIR of the carbonyl region detected only absorbtions characteristic of ester and carboxylate salt. Acid value of the product was 0.074 mmol/g.
  • Example 10 Product of Example 3 (199.33 g) was dissolved in Shellsol ABTM (256.48 g) and reacted at an initial temperature of 85°C with KOH (39.39 g) . A clear solution was obtained within one hour.
  • Example 10
  • Example 4 Product of Example 4 (603.70 g, 1.28 mol acid equivalent) and Shellsol ABTM (323.32 g) were charged to the reactor described previously. The contents were warmed to 85°C and KOH flake (79.69 g, 1.28 mol base) was added. Within one hour virtually all of the KOH had dissolved. The oil temperature was reduced to 50°C and the mixture left to stir overnight. FTIR of the carbonyl stretching region showed peaks ascribable to ester at 1715 cm "1 and carboxylate salt at 1575 cm "1 . Titration against lithium methoxide solution showed the solution to have 0.1 mmol H + /g.
  • Example 5 The product of Example 5 (286.22 g, 0.71 mol acid equivalent) and Shellsol ABTM (229.95 g) were charged to the reactor used previously. The contents were stirred and warmed to 56°C, forming a homogenous solution. KOH flake (23.57 g, 0.378 mol) was then added causing an exotherm to 67°C over about 20 minutes. The solution was allowed to cool back to 56°C and a second portion of KOH flake (21.07 g, 0.338 mol) was added. The mixture was left to stir overnight at 56°C. A few small flakes of KOH remained, lithium methoxide titration showed the acid value of the solution to be 0.12 mmolH + /g.
  • Example 12 Example 12
  • Hemi-ester of isopropanol with poly (butenyl) succinic anhydride was prepared as described in Example 4, a final acidity of 2.20 mmol/g versus 2.12 theoretical was found.
  • the hemi-ester (498.23 g) and ShellsolTM AB (358.56 g) were charged to the SoverelTM reactor set-up and heated to 70 °C internal (oil temperature 90 °C) before charging anhydrous Sr(OH) 2 (96% active 69.60 g, 549 mmol) and approximately 5cm 3 of water.
  • the mixture was heated and stirred overnight to yield a faintly cloudy, brown solution. Filtration through a short column of CeliteTM produced a clear solution of acid value 0.1 mmol/g.
  • the treat rate for this formulation is such that 1000 mg/kg provides 15 ppm K.
  • Example 10 Material prepared as in Example 10 was blended into a standard European diesel fuel such that the potassium content of the fuel was 15 ppm m/m. Emissions tests were then performed in a modern IDI engine and according to the standard EEC 91/114 protocol consisting of City and Extra-Urban Dive Cycles. Additional 'Hot-start' Urban Drive Cycles were incorporated for illustrative purposes. The values obtained therein are not reflected in the 'Overall' result, which is calculated in the normal way .
  • the engine was mounted on a pallet arrangement which was equipped with appropriate heat exchangers, electrical connections and connectors for instrumentation signals. This pallet arrangement was then connected to the engine test bench.
  • the engine dynamometer was a Froude AG150 eddy current machine controlled by the CP Engineering Cadet system. , The engine temperatures were controlled automatically by suitable 3 -term controllers integrated into the secondary coolant system supplies.
  • the test bench was controlled, and data was logged using a CP Engineering Cadet system.
  • Fuel flow was measured using an AVL 730 gravimetric fuel balance. The difference of the mass of fuel, in a vessel, is monitored over a set period of time. For this work fuel flow was measured over a 20 second interval .
  • the engine exhaust system was modified to allow ready interchange of a centre section which could incorporate a selection of DPFs.
  • a NoToxTM SiC wall-flow DPF was used for the work reported here.
  • the base fuel used throughout the testing reported here was an EN 590 specification fuel labelled as SD2. Analysis of the fuel is given below.
  • the engine was run at a series of constant speed/load conditions over 12 to 16 hours per test fuel, as detailed below.
  • Gauge pressure in the exhaust downpipe in advance of the DPF was measured using a pressure transducer at 1Hz with logging of average readings over 10 second periods.
  • Regeneration of the DPF, i.e. burnoff of the trapped material was detected as a decrease in pressure. Comparison of mean pressure or of mean pressure plus two standard deviations therein is thus a direct comparison of the relative efficiency of any two additives present in the fuel at causing burnoff of trapped material .
  • Example 10 Overall, the product of Example 10 can be seen to be at least as effective as the previously employed material.

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  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

La présente invention porte sur un composé de la formule (I) dans laquelle R1 est un groupe éventuellement substitué, saturé ou insaturé, à chaîne droite ou ramifiée, de préférence un groupe alcényle ou poly(alcényle). Un élément de R2 et R3 représente un atome d'hydrogène et l'autre élément de R2 et R3 représente un groupe alkyle à chaîne droite ou ramifiée. R4 représente un atome d'hydrogène ou un groupe alkyle à chaîne droite ou ramifiée, de préférence un atome d'hydrogène; ou, dans une autre version, R1 et R4 peuvent être réunis de façon à former un noyau, éventuellement substitué, à 5 ou 6 éléments. L'invention porte également sur des sels métalliques et des complexes de ceux-ci, des isomères optiques et leurs diastéréoisomères.
PCT/GB1999/002751 1998-08-21 1999-08-19 Additifs pour carburants WO2000011119A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU54363/99A AU5436399A (en) 1998-08-21 1999-08-19 Fuel additives
EP99940373A EP1112339A1 (fr) 1998-08-21 1999-08-19 Additifs pour carburants

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9818323.9 1998-08-21
GBGB9818323.9A GB9818323D0 (en) 1998-08-21 1998-08-21 Fuel additives

Publications (1)

Publication Number Publication Date
WO2000011119A1 true WO2000011119A1 (fr) 2000-03-02

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EP (1) EP1112339A1 (fr)
AU (1) AU5436399A (fr)
GB (1) GB9818323D0 (fr)
WO (1) WO2000011119A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002002720A2 (fr) * 2000-07-03 2002-01-10 The Associated Octel Company Limited Additifs de carburant
LT5161B (lt) 2003-12-12 2004-09-27 Rimvydas JASINAVIČIUS Degalų priedas taurinto etanolio pagrindu
EP1512736B1 (fr) 2003-09-05 2018-05-02 Infineum International Limited Compositions d'additifs stabilisées pour carburants diesel

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB712431A (en) * 1950-11-30 1954-07-21 George Hugo Von Fuchs Improvements in or relating to rust preventing compositions and process
US3088813A (en) * 1959-07-08 1963-05-07 Du Pont Antiknock motor fuels
US3223497A (en) * 1961-08-31 1965-12-14 Standard Oil Co Gasoline composition containing a multipurpose additive
US3485858A (en) * 1968-04-03 1969-12-23 Mobil Oil Corp Metal alkyl,or alkoxy metal alkyl,ester tetrapropenylsuccinates
US3632510A (en) * 1963-04-23 1972-01-04 Lubrizol Corp Mixed ester-metal salts and lubricants and fuels containing the same
DE2517103A1 (de) * 1975-04-18 1976-11-04 Veba Chemie Ag Verbesserung der filtrierbarkeit von dieselkraftstoffen und heizoelen
US4234435A (en) * 1979-02-23 1980-11-18 The Lubrizol Corporation Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation
US4652611A (en) * 1982-04-12 1987-03-24 Mitsubishi Chemical Industries Limited Low-temperature fluidity improver
WO1992020765A1 (fr) * 1991-05-13 1992-11-26 The Lubrizol Corporation Carburants diesel contenant des complexes organometalliques
EP0765857A1 (fr) * 1994-06-13 1997-04-02 Mitsubishi Rayon Co., Ltd. Derive d'acide carboxylique optiquement actif a substitution alpha et procede de production dudit derive

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB712431A (en) * 1950-11-30 1954-07-21 George Hugo Von Fuchs Improvements in or relating to rust preventing compositions and process
US3088813A (en) * 1959-07-08 1963-05-07 Du Pont Antiknock motor fuels
US3223497A (en) * 1961-08-31 1965-12-14 Standard Oil Co Gasoline composition containing a multipurpose additive
US3632510A (en) * 1963-04-23 1972-01-04 Lubrizol Corp Mixed ester-metal salts and lubricants and fuels containing the same
US3485858A (en) * 1968-04-03 1969-12-23 Mobil Oil Corp Metal alkyl,or alkoxy metal alkyl,ester tetrapropenylsuccinates
DE2517103A1 (de) * 1975-04-18 1976-11-04 Veba Chemie Ag Verbesserung der filtrierbarkeit von dieselkraftstoffen und heizoelen
US4234435A (en) * 1979-02-23 1980-11-18 The Lubrizol Corporation Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation
US4652611A (en) * 1982-04-12 1987-03-24 Mitsubishi Chemical Industries Limited Low-temperature fluidity improver
WO1992020765A1 (fr) * 1991-05-13 1992-11-26 The Lubrizol Corporation Carburants diesel contenant des complexes organometalliques
EP0765857A1 (fr) * 1994-06-13 1997-04-02 Mitsubishi Rayon Co., Ltd. Derive d'acide carboxylique optiquement actif a substitution alpha et procede de production dudit derive

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002002720A2 (fr) * 2000-07-03 2002-01-10 The Associated Octel Company Limited Additifs de carburant
WO2002002720A3 (fr) * 2000-07-03 2002-10-24 Ass Octel Additifs de carburant
GB2381789A (en) * 2000-07-03 2003-05-14 Ass Octel Fuel additives
GB2381789B (en) * 2000-07-03 2004-06-30 Ass Octel Fuel additives
EP1512736B1 (fr) 2003-09-05 2018-05-02 Infineum International Limited Compositions d'additifs stabilisées pour carburants diesel
LT5161B (lt) 2003-12-12 2004-09-27 Rimvydas JASINAVIČIUS Degalų priedas taurinto etanolio pagrindu

Also Published As

Publication number Publication date
EP1112339A1 (fr) 2001-07-04
GB9818323D0 (en) 1998-10-14
AU5436399A (en) 2000-03-14

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