EP0487255A1 - Composition and process for inhibiting and removing carbonaceous deposits - Google Patents

Composition and process for inhibiting and removing carbonaceous deposits Download PDF

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Publication number
EP0487255A1
EP0487255A1 EP91310512A EP91310512A EP0487255A1 EP 0487255 A1 EP0487255 A1 EP 0487255A1 EP 91310512 A EP91310512 A EP 91310512A EP 91310512 A EP91310512 A EP 91310512A EP 0487255 A1 EP0487255 A1 EP 0487255A1
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Prior art keywords
hydrocarbon fuel
cleaning agent
aminopropyl
composition
imidazolidinone
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EP91310512A
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German (de)
French (fr)
Inventor
Sian Catrin Clark
Neil Angus Greener
Gareth Charles Jeffrey
Peyman Ostovar
Angus Joseph Dickson Reid
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BP Chemicals Ltd
BP PLC
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BP Chemicals Ltd
BP PLC
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
    • 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
    • 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
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—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
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • 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

Definitions

  • the present invention relates to the inhibition of formation of carbonaceous deposits and also to their removal from surfaces by the use of a cleaning agent.
  • US 2 956 910 discloses a method for removing combustion deposits from the combustion chamber of an internal combustion engine by contacting the deposits with N-methyl-2-pyrrolidone and then removing the loosened deposits.
  • US 3 144 311 discloses the use of an alkyl substituted 2-pyrrolidone in fuel compositions for internal combustion engines to reduce deposition.
  • the addition of the pyrrolidone derivatives to gasoline to reduce the increase in octane number requirement of the engine with use is disclosed.
  • pyrrolidone derivatives disclosed are N-methyl-2-pyrrolidone and N-beta-ethylene acetate-2-pyrrolidone. The latter compound gave no reduction in octane number requirement.
  • US 3 301 784 discloses certain N-hydrocarbyl C-alkyl substituted 2-pyrrolidones (described in the specification as pyrrolidinones).
  • the substituents on the N atom disclosed include methyl, decyl, cyclohexyl and phenyl. No substituted hydrocarbyl substituents are disclosed.
  • the compounds are used in gasolines to reduce deposit formation in the engine combustion chamber.
  • a process for removing a carbonaceous deposit from a surface comprises contacting the deposit with a cleaning agent selected from 1-(3-aminopropyl)-2-pyrrolidinone, 1-(3-aminopropyl) imidazole, N-hydroxyethyl imidazolidinone, N-aminoethyl-imidazolidinone and 2-(2-aminoethylamino) ethanol.
  • a cleaning agent selected from 1-(3-aminopropyl)-2-pyrrolidinone, 1-(3-aminopropyl) imidazole, N-hydroxyethyl imidazolidinone, N-aminoethyl-imidazolidinone and 2-(2-aminoethylamino) ethanol.
  • the process of the present invention may be applied to carbonaceous deposits resulting from the thermal decomposition of carbon-containing compounds, for example, as a separate cleaning step after a process which produces carbonaceous deposits.
  • the cleaning agent may be included in a feed to a process giving rise the carbonaceous deposits to act as a deposit inhibitor.
  • the cleaning agent can be included as a deposit inhibitor in a fuel to an internal combustion engine, in particular in a gasoline fuel.
  • a hydrocarbon fuel composition suitable for an internal combustion engine comprises a hydrocarbon fuel and, as a cleaning agent for carbonaceous deposits a compound selected from 1-(3-aminopropyl)-2-pyrrolidinone, 1-(3-aminopropyl) imidazole, N-hydroxyethyl imidazolidinone, N-aminoethyl-imidazolidinone and 2-(2-aminoethylamino) ethanol.
  • Suitable amounts of the cleaning agent are from 10 to 5000 ppm by weight, preferably from 50 to 2000 ppm based on the weight of the composition.
  • the abbreviation ppm means parts per million.
  • the present invention also provides a process for the operation of an internal combustion engine comprising supplying a hydrocarbon fuel to the engine and to reduce carbonaceous deposits in the engine and/or the inlet system thereof the hydrocarbon fuel supplied to the engine contains a cleaning agent selected from 1-(3-aminopropyl)-2-pyrrolidinone, 1-(3-aminopropyl) imidazole, N-hydroxyethyl imidazolidinone, N-aminoethyl-imidazolidinone and 2-(2-aminoethylamino) ethanol.
  • a cleaning agent selected from 1-(3-aminopropyl)-2-pyrrolidinone, 1-(3-aminopropyl) imidazole, N-hydroxyethyl imidazolidinone, N-aminoethyl-imidazolidinone and 2-(2-aminoethylamino) ethanol.
  • APP 1-(3-aminopropyl)-2-pyrrolidinone hereafter referred to as APP is a commercially available compound, obtainable from Aldrich Chemical Company Limited and is liquid at normal ambient temperatures and can thus be used undiluted. In general it will be preferred to use APP in admixture with a liquid diluent, preferably a diluent which is miscible with APP at the treatment temperature.
  • Mixtures of APP and diluent containing for example 5% to 40% by weight based on total weight of diluent and APP may be used for removal of deposits which have already formed.
  • the deposit is preferably treated with the cleaning liquid at moderately elevated temperatures.
  • suitable temperatures are those in the range 100 °C to 200 °C or preferably 150 °C to 170 °C.
  • the duration of the treatment will depend on the amount of deposit but may for example range from 1 to 30 hours, preferably 10 to 25 hours. In the case of a fuel additive the treatment would be continuous.
  • the cleaning agent can conveniently be dissolved or dispersed in a carrier such as a lubricating oil, a hydrocarbon polymer or a polyether.
  • a carrier such as a lubricating oil, a hydrocarbon polymer or a polyether.
  • Suitable carriers are disclosed, for example, in UK Patent No. 1346765, US Patent No. 4877416 and European Patent No. 62940.
  • the carrier and the cleaning agent can be mixed to form a concentrate and the latter can then be added to the hydrocarbon fuel.
  • the carrier will have a viscosity of between 20 and 2500 centistokes at 20°C and can be a polymer of molecular weight from 300 to 5000.
  • Particularly suitable polymers are polyalkylene glycols such as those of polyoxyethylene and polyoxypropylene and their copolymers.
  • Other polymers that can be used are polymers and copolymers of a C2 to C6 monolefin, preferably having a molecular weight from 300 to 5000, more preferably 500 to 2000.
  • the carrier can be present in the amount from 50 to 20,000 ppm, preferably 200 to 10,000 ppm based on the weight of the fuel composition.
  • a concentrate suitable for use in a hydrocarbon fuel in the gasoline boiling range comprises 1 to 40% of a cleaning agent as specified above and up to 95% of a carrier selected from hydrocarbon polymers, polyethers, and lubricating oils, the % being by weight based on the total composition of the concentrate.
  • the concentrate can contain up to 75% of a fuel compatible diluent the % being by weight of the total composition of concentrate.
  • the diluent can be one boiling in the range 50 to about 232°C.
  • Suitable diluents are methanol, ethanol, propanol, methyl tertiary butyl ether and ethylene glycol monobutyl ether.
  • alkanes can be used such as heptane but preferably an aromatic hydrocarbon such as toluene or xylene can be used.
  • a deposit was generated by thermally decomposing a fully-formulated lubricant oil on a stainless steel plate maintained at 270°C.
  • the lubricant oil was a commercially available product sold by BP as Visco 2000.
  • the deposit was generated as follows:
  • the plate 25 mm ⁇ 75 mm was coated with the oil and heated at 270°C in air for 2 hours. Then the metal plate carrying the deposit was immersed in 80 g of a mixture in the weight ratio of 1:1 of (a) the lubricant used in generating the deposit and (b) a 1200 N base oil, the mixture containing 30 % weight/weight APP. The liquid mixture in which the surface carrying the deposit was immersed was heated to 160°C and allowed to remain at that temperature for 18 hours.
  • the amount of any removal of deposit from a metal surface was assessed by visual inspection. It was rated at 5 on a scale from 0 to 5. A rating of 5 corresponded to about 90% removal.
  • Example 2 An experiment was carried out as in Example 1 except that the amount of APP used was 6% by weight.
  • the amount of deposit removed was rated at about 2.5 corresponding to about 40% removal of deposit.
  • Example 1 Experiments were carried out as in Example 1 using a variety of heterocyclic or nitrogen containing compound:: in place of APP.
  • the additive was not soluble but melted at the temperature used and could therefore be used as a dispersion.
  • the amount used was the maximum that could be either dissolved or dispersed in the lubricant/base oil medium.
  • the amount of additive introduced was between 6% and 30% by weight.
  • the cleaning ability of the compounds was assessed visually on a scale from 0 to 5 as in Example 1 above.
  • the following compounds were assessed at a cleaning value of 1, namely The following compounds were assessed as being a cleaning value of 2, namely The following compounds were assessed as having a cleaning value of 3, namely
  • the cleaning agents having a cleaning value of 4 and 5 identified above are individually dispersed in a polyethylene glycol carrier of molecular weight 2000 to provide five dispersions containing 20% by weight of cleaning agent based on the total weight of the dispersion.
  • the dispersion is then added to an unleaded motor gasoline of octane number 97 to give a gasoline containing 500 ppm of cleaning agent.
  • a series of tests are carried out on a Mercedes 102E engine. Firstly the engine is run for 60 hours using the base fuel, ie, the gasoline with no cleaning agent added and the inlet valves examined visually. Carbonaceous deposits are identified.
  • the engine is then run for a further 60 hours with the same gasoline but containing 500 ppm of the cleaning agent prepared as described above and the inlet valves examined visually. A reduction in the carbonaceous deposits is observed.
  • the operation of the engine over the 60 hour cycle is as follows: the engine is run for 4 minutes at 1500 RPM and then 6 minutes at 4500 RPM and this procedure repeated over the entire 60 hour cycle.

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Abstract

A hydrocarbon fuel composition suitable for an internal combustion engine comprises a hydrocarbon fuel and as a cleaning agent for carbonaceous deposits a compound selected from 1-(3-aminopropyl)-2-pyrrolidinone, 1-(3 aminopropyl) imidazole, N-hydroxyethyl imidazolidinone,
N-aminoethyl-imidazolidinone and 2-(2-aminoethylamino) ethanol. The fuel can be a gasoline and include a carrier in which the cleaning agent is first dispersed before blending with the fuel. The carrier can be a lubricating oil, a polyether or a polymer of a C₂ to C₆ monoolefin.

Description

  • The present invention relates to the inhibition of formation of carbonaceous deposits and also to their removal from surfaces by the use of a cleaning agent.
  • US 2 956 910 discloses a method for removing combustion deposits from the combustion chamber of an internal combustion engine by contacting the deposits with N-methyl-2-pyrrolidone and then removing the loosened deposits.
  • US 3 144 311 discloses the use of an alkyl substituted 2-pyrrolidone in fuel compositions for internal combustion engines to reduce deposition. In particular the addition of the pyrrolidone derivatives to gasoline to reduce the increase in octane number requirement of the engine with use is disclosed. Among pyrrolidone derivatives disclosed are N-methyl-2-pyrrolidone and N-beta-ethylene acetate-2-pyrrolidone. The latter compound gave no reduction in octane number requirement.
  • US 3 301 784 discloses certain N-hydrocarbyl C-alkyl substituted 2-pyrrolidones (described in the specification as pyrrolidinones). The substituents on the N atom disclosed include methyl, decyl, cyclohexyl and phenyl. No substituted hydrocarbyl substituents are disclosed. The compounds are used in gasolines to reduce deposit formation in the engine combustion chamber.
  • It is an object of the present invention to provide alternative cleaning agents for the inhibition of formation and the removal of carbonaceous deposits from surfaces.
  • According to one aspect of present invention a process for removing a carbonaceous deposit from a surface comprises contacting the deposit with a cleaning agent selected from 1-(3-aminopropyl)-2-pyrrolidinone, 1-(3-aminopropyl) imidazole, N-hydroxyethyl imidazolidinone, N-aminoethyl-imidazolidinone and 2-(2-aminoethylamino) ethanol.
  • The process of the present invention may be applied to carbonaceous deposits resulting from the thermal decomposition of carbon-containing compounds, for example, as a separate cleaning step after a process which produces carbonaceous deposits. Alternatively the cleaning agent may be included in a feed to a process giving rise the carbonaceous deposits to act as a deposit inhibitor. Thus the cleaning agent can be included as a deposit inhibitor in a fuel to an internal combustion engine, in particular in a gasoline fuel.
  • Thus according to the present invention a hydrocarbon fuel composition suitable for an internal combustion engine comprises a hydrocarbon fuel and, as a cleaning agent for carbonaceous deposits a compound selected from 1-(3-aminopropyl)-2-pyrrolidinone, 1-(3-aminopropyl) imidazole, N-hydroxyethyl imidazolidinone, N-aminoethyl-imidazolidinone and 2-(2-aminoethylamino) ethanol.
  • Suitable amounts of the cleaning agent are from 10 to 5000 ppm by weight, preferably from 50 to 2000 ppm based on the weight of the composition. The abbreviation ppm means parts per million.
  • The present invention also provides a process for the operation of an internal combustion engine comprising supplying a hydrocarbon fuel to the engine and to reduce carbonaceous deposits in the engine and/or the inlet system thereof the hydrocarbon fuel supplied to the engine contains a cleaning agent selected from 1-(3-aminopropyl)-2-pyrrolidinone, 1-(3-aminopropyl) imidazole, N-hydroxyethyl imidazolidinone, N-aminoethyl-imidazolidinone and 2-(2-aminoethylamino) ethanol.
  • 1-(3-aminopropyl)-2-pyrrolidinone hereafter referred to as APP is a commercially available compound, obtainable from Aldrich Chemical Company Limited and is liquid at normal ambient temperatures and can thus be used undiluted. In general it will be preferred to use APP in admixture with a liquid diluent, preferably a diluent which is miscible with APP at the treatment temperature.
  • Mixtures of APP and diluent containing for example 5% to 40% by weight based on total weight of diluent and APP may be used for removal of deposits which have already formed.
  • The deposit is preferably treated with the cleaning liquid at moderately elevated temperatures. Examples of suitable temperatures are those in the range 100 °C to 200 °C or preferably 150 °C to 170 °C.
  • The duration of the treatment will depend on the amount of deposit but may for example range from 1 to 30 hours, preferably 10 to 25 hours. In the case of a fuel additive the treatment would be continuous.
  • For use in fuels the cleaning agent can conveniently be dissolved or dispersed in a carrier such as a lubricating oil, a hydrocarbon polymer or a polyether. Suitable carriers are disclosed, for example, in UK Patent No. 1346765, US Patent No. 4877416 and European Patent No. 62940. The carrier and the cleaning agent can be mixed to form a concentrate and the latter can then be added to the hydrocarbon fuel.
  • Conveniently the carrier will have a viscosity of between 20 and 2500 centistokes at 20°C and can be a polymer of molecular weight from 300 to 5000. Particularly suitable polymers are polyalkylene glycols such as those of polyoxyethylene and polyoxypropylene and their copolymers. Other polymers that can be used are polymers and copolymers of a C₂ to C₆ monolefin, preferably having a molecular weight from 300 to 5000, more preferably 500 to 2000.
  • The carrier can be present in the amount from 50 to 20,000 ppm, preferably 200 to 10,000 ppm based on the weight of the fuel composition.
  • According to another aspect of the invention a concentrate suitable for use in a hydrocarbon fuel in the gasoline boiling range comprises 1 to 40% of a cleaning agent as specified above and up to 95% of a carrier selected from hydrocarbon polymers, polyethers, and lubricating oils, the % being by weight based on the total composition of the concentrate.
  • The concentrate can contain up to 75% of a fuel compatible diluent the % being by weight of the total composition of concentrate. The diluent can be one boiling in the range 50 to about 232°C. Suitable diluents are methanol, ethanol, propanol, methyl tertiary butyl ether and ethylene glycol monobutyl ether. Alternatively alkanes can be used such as heptane but preferably an aromatic hydrocarbon such as toluene or xylene can be used.
  • The invention will now be described by reference to the following examples and comparative tests.
    • Example 1
  • A deposit was generated by thermally decomposing a fully-formulated lubricant oil on a stainless steel plate maintained at 270°C. The lubricant oil was a commercially available product sold by BP as Visco 2000. The deposit was generated as follows:
  • The plate 25 mm × 75 mm was coated with the oil and heated at 270°C in air for 2 hours. Then the metal plate carrying the deposit was immersed in 80 g of a mixture in the weight ratio of 1:1 of (a) the lubricant used in generating the deposit and (b) a 1200 N base oil, the mixture containing 30 % weight/weight APP. The liquid mixture in which the surface carrying the deposit was immersed was heated to 160°C and allowed to remain at that temperature for 18 hours.
  • The amount of any removal of deposit from a metal surface was assessed by visual inspection. It was rated at 5 on a scale from 0 to 5. A rating of 5 corresponded to about 90% removal.
    • Example 2
  • An experiment was carried out as in Example 1 except that the amount of APP used was 6% by weight.
  • The amount of deposit removed was rated at about 2.5 corresponding to about 40% removal of deposit.
    • Comparative Test and Example 3
  • Experiments were carried out as in Example 1 using a variety of heterocyclic or nitrogen containing compound:: in place of APP. In some cases the additive was not soluble but melted at the temperature used and could therefore be used as a dispersion. The amount used was the maximum that could be either dissolved or dispersed in the lubricant/base oil medium. In general the amount of additive introduced was between 6% and 30% by weight. The cleaning ability of the compounds was assessed visually on a scale from 0 to 5 as in Example 1 above.
  • The following compounds were found to give no cleaning, namely
    Figure imgb0001
    Figure imgb0002
    Figure imgb0003
  • The following compounds were assessed at a cleaning value of 1, namely
    Figure imgb0004
    Figure imgb0005
    The following compounds were assessed as being a cleaning value of 2, namely
    Figure imgb0006
     The following compounds were assessed as having a cleaning value of 3, namely
    Figure imgb0007
    • Example 3
  • The following compounds were assessed as having a cleaning value of 4, namely
    Figure imgb0008
    Figure imgb0009
    • Example 4
  • and the following were assessed at between 4 and 5, namely,
    Figure imgb0010
    • Example 5
  • and assessed at 5 was
    Figure imgb0011
  • These results demonstrate the superior cleaning ability of the compounds according to the invention, namely
    1-(3-aminopropyl)-2-pyrrolidinone, 1-(3 aminopropyl) imidazole, N-hydroxyethyl imidazolidinone, N-aminoethyl-imidazolidinone and 2-(2-aminoethylamino) ethanol.
    • Example 6
  • The cleaning agents having a cleaning value of 4 and 5 identified above are individually dispersed in a polyethylene glycol carrier of molecular weight 2000 to provide five dispersions containing 20% by weight of cleaning agent based on the total weight of the dispersion.
  • The dispersion is then added to an unleaded motor gasoline of octane number 97 to give a gasoline containing 500 ppm of cleaning agent. A series of tests are carried out on a Mercedes 102E engine. Firstly the engine is run for 60 hours using the base fuel, ie, the gasoline with no cleaning agent added and the inlet valves examined visually. Carbonaceous deposits are identified.
  • The engine is then run for a further 60 hours with the same gasoline but containing 500 ppm of the cleaning agent prepared as described above and the inlet valves examined visually. A reduction in the carbonaceous deposits is observed.
  • The operation of the engine over the 60 hour cycle is as follows: the engine is run for 4 minutes at 1500 RPM and then 6 minutes at 4500 RPM and this procedure repeated over the entire 60 hour cycle.

Claims (10)

  1. A hydrocarbon fuel composition suitable for an internal combustion engine comprising a hydrocarbon fuel and, as a cleaning agent for carbonaceous deposits, a compound selected from 1-(3-aminopropyl)-2-pyrrolidinone, 1-(3 aminopropyl) imidazole, N-hydroxyethyl imidazolidinone, N-aminoethyl-imidazolidinone and 2-(2-aminoethylamino) ethanol.
  2. A hydrocarbon fuel composition as claimed in Claim 1 wherein the hydrocarbon fuel is a gasoline and the amount of the cleaning agent is from 10 to 5000 ppm by weight based on the weight of the composition.
  3. A hydrocarbon fuel composition as claimed in Claim 2 which composition further comprises a carrier for the cleaning agent, the carrier being selected from hydrocarbon polymers, polyethers and lubricating oils.
  4. A hydrocarbon fuel composition as claimed in Claim 3 wherein the carrier is present in an amount from 50 to 20,000 ppm by weight based on the weight of the composition.
  5. A concentrate suitable for use in a hydrocarbon fuel in the gasoline boiling range comprising 1 to 40% by weight of a cleaning agent specified in Claim 1 and up to 95% of a carrier selected from hydrocarbon polymers, polyethers and lubricating oils, the % being by weight based on the total composition of the concentrate.
  6. A concentrate as claimed in Claim 5 which further contains up to 75% of a fuel compatible diluent.
  7. A process for removing a carbonaceous deposit from a surface which comprises by contacting the deposit with a cleaning agent selected from 1-(3-aminopropyl)-2-pyrrolidinone, 1-(3 aminopropyl) imidazole, N-hydroxyethyl imidazolidinone,
    N-aminoethyl-imidazolidinone and 2-(2-aminoethylamino) ethanol.
  8. A process for the operation of an internal combustion engine which process comprises supplying a hydrocarbon fuel to the engine and wherein to reduce carbonaceous deposits in the engine and/or the inlet system thereof the hydrocarbon fuel supplied to the engine contains a cleaning agent selected from
    1-(3-aminopropyl)-2-pyrrolidinone, 1-(3 aminopropyl) imidazole, N-hydroxyethyl imidazolidinone, N-aminoethyl-imidazolidinone and 2-(2-aminoethylamino) ethanol.
  9. A process as claimed in Claim 8 whereas the hydrocarbon fuel is a gasoline.
  10. A process as claimed in Claim 8 wherein the hydrocarbon fuel is a diesel fuel.
EP91310512A 1990-11-22 1991-11-14 Composition and process for inhibiting and removing carbonaceous deposits Ceased EP0487255A1 (en)

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GB909025387A GB9025387D0 (en) 1990-11-22 1990-11-22 Process for removing carbonaceous deposits
GB9025387 1990-11-22

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DE4328276A1 (en) * 1992-08-24 1994-03-03 Toyota Motor Co Ltd Fuel combustion in e.g. petrol or diesel engines - forms an inner shell as soot is developed with other gas components to give a chemical reaction without an outer shell formation
EP0608981A2 (en) * 1993-01-11 1994-08-03 Nec Corporation Connection-oriented congestion controller for common channel signaling network
EP0757092A1 (en) * 1995-07-31 1997-02-05 Tonen Corporation Gas oil
WO2001021739A1 (en) * 1999-09-20 2001-03-29 Exxonmobil Research And Engineering Company Fuel composition with improved lubricity performance
WO2003050212A2 (en) * 2001-12-11 2003-06-19 Exxonmobil Research And Engineering Company Gasoline additives such as butyrolactam for reducing the amount of internal combustion engine deposits
US7226489B2 (en) 2001-12-12 2007-06-05 Exxonmobil Research And Engineering Company Gasoline additives for reducing the amount of internal combustion engine intake valve deposits and combustion chamber deposits
WO2015059206A1 (en) * 2013-10-24 2015-04-30 Shell Internationale Research Maatschappij B.V. Liquid fuel compositions

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EP0608981A2 (en) * 1993-01-11 1994-08-03 Nec Corporation Connection-oriented congestion controller for common channel signaling network
EP0608981A3 (en) * 1993-01-11 1995-08-23 Nec Corp Connection-oriented congestion controller for common channel signaling network.
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WO2003050212A2 (en) * 2001-12-11 2003-06-19 Exxonmobil Research And Engineering Company Gasoline additives such as butyrolactam for reducing the amount of internal combustion engine deposits
WO2003050212A3 (en) * 2001-12-11 2003-10-16 Exxonmobil Res & Eng Co Gasoline additives such as butyrolactam for reducing the amount of internal combustion engine deposits
US7204863B2 (en) 2001-12-11 2007-04-17 Exxonmobil Research And Engineering Company Gasoline additives for reducing the amount of internal combustion engine intake valve deposits and combustion chamber deposits
US7226489B2 (en) 2001-12-12 2007-06-05 Exxonmobil Research And Engineering Company Gasoline additives for reducing the amount of internal combustion engine intake valve deposits and combustion chamber deposits
WO2015059206A1 (en) * 2013-10-24 2015-04-30 Shell Internationale Research Maatschappij B.V. Liquid fuel compositions

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NZ240685A (en) 1993-03-26
GB9025387D0 (en) 1991-01-09

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