Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • 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
• • 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
  • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
  • C10L1/2406—Organic compounds containing sulfur, selenium and/or tellurium mercaptans; hydrocarbon sulfides
  • C10L1/2412—Organic compounds containing sulfur, selenium and/or tellurium mercaptans; hydrocarbon sulfides sulfur bond to an aromatic radical
• • 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
  • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
  • C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
  • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
  • F02B3/00—Engines characterised by air compression and subsequent fuel addition
  • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
  • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
  • F02B77/00—Component parts, details or accessories, not otherwise provided for
  • F02B77/04—Cleaning of, preventing corrosion or erosion in, or preventing unwanted deposits in, combustion engines

Definitions

• This invention concerns a diesel fuel having a reduced tendency to form deposits in and around the combustion chambers of diesel engines.
• Oxidation of fuel and incomplete combustion results in deposition of highly carbonaceous material in and around the combustion chambers of internal combustion engines.
• U.S. Patents No. 3008813 and 3346353 concern a petroleum distillate fuel containing an ashless oil soluble polymeric dispersant stabilising additive and a dialkyl dimethyl ammonium chloride or a dialkyl dimethyl ammonium nitrite, respectively. These additives are adapted to prevent the formation of persistent haze and stable emulsions when the petroleum distillate fuel is contacted with water during handling and storage.
• U.S. Patent No 3397970 relates to a petroleum distillate oil containing a pour point depressing amount of a copolymer of ethylene and an olefinically unsaturated aliphatic ester monomer (for example vinyl acetate) said copolymer tending to promote the formation of water haze in said oil, and as an inhibitor of said haze a dimer of linoleic acid and quaternary ammonium salt selected from dicocyl dimethyl ammonium chloride and dicocyl dimethyl ammonium nitrite.
• U.S. Patent No 3493354 discloses a diesel fuel additive containing a major amount of an organic barium compound in combination with a minor amount of a quaternary ammonium salt.
• the additive promotes the combustion of the fuel, thereby reducing the proportion of unburned hydrocarbons and suspended soot particles in the exhaust gases of diesel engines.
• the quaternary ammonium salts serves to prevent the extraction of barium by water with which the additive or fuel containing the additive may come into contact.
• United Kingdom Patents 973826 and 1076497 relate to using quaternary ammonium compounds, particularly nitrates as distillate fuel stabilisers whereas United Kingdom Patent 1432265 proposes their use as antistatic agents together with polysulphones.
• a diesel fuel composition for use in an indirect injection engine comprises a diesel fuel and a minor proportion by weight of a quaternary ammonium salt soluble therein.
• the four residues connected to the quaternary nitrogen atom of the quaternary ammonium salt are essentially hydrocarbyl residues. These residues may be similar or dissimilar. They may be substituted with functional groups or have incorporated therein functional groups as parts of the hydrocarbyl chain.
• one or two of these residues contain at least 6 carbon atoms while the remaining residues contain less than 6 carbon atoms. It is preferred that one of the residues contains at least 8 carbon atoms while the remaining residues contain less than 6 carbon atoms.
• hydrocarbyl residues are alkyl groups, alkenyl groups, aryl groups or alkaryl groups.
• alkyl groups containing less than 6 carbon atoms are methyl, ethyl, isopropyl, propyl and butyl groups.
• alkyl groups containing more than 6 carbon atoms are dodecyl (lauryl), tetradecyl (myristyl), hexadecyl (cetyl) and octadecyl (stearyl) groups.
• alkenyl groups containing more than 6 carbon atoms are dodecenyl, tetradecenyl, octadecenyl (oleyl), and octadecadienyl (linoleyl) grpups.
• the residues containing more than 6 carbon atoms can be derived from natural fats and oils, for example coconut oil, soya bean oil, animal tallow and the like. In such instances these residues will consist essentially of mixed alkyl groups containing 8 to 22 carbon atoms.
• the hydrocarbyl residues may contain functional groups.
• functional groups which may be present in the residues are hydroxy, halide, ester, amide, ether, amine, and sulphide functions.
• the anionic radical is a strong acid radical.
• strong acid radicals useful according to the invention are nitrate, sulphate, ethosulphate, sulphonate (both alkyl and alkylaryl), sulphurised phenate, carboxylate, and borate. It is also possible to employ mixtures of anionic radicals.
• the quaternary ammonium compound is a sulphonate it can be made from:
• the sulphonic acids are typically obtained by sulphonation of alkyl substituted aromatic hydrocarbons, such as those obtained from the fractionation of petroleum by distillation and/or extraction, or by the alkylation of an aromatic hydrocarbon , for example, benzene, toluene, xylene, naphthalene, diphenyl.
• the alkylation may be carried out in the presence of a catalyst with alkylating agents having from about 3 to more than 30 carbon atoms, such as, for example, haloparaffins, olefins that may be obtained by dehydrogenation of paraffins, polyolefins, or, for example, polymers of ethylene, propylene, butene, etc.
• the alkaryl sulphonates usually contain from about 9 to about 20 or more carbon atoms, preferably from about 16 to about 50 carbon atoms per alkyl substituted aromatic moiety.
• Quaternary ammonium sulphurised phenates are synthesised from sulphurised alkylphenols which have the general structure: where R is an alkyl radical, n is an integer from 0 to 4 and x is an integer from 1 to 4.
• the average number of carbon atoms in all of the R groups is preferably at least about 9 in order to ensure adequate solubility in oil.
• the individual R groups may contain from 5 to 40, preferably 8 to 20 carbon atoms.
• Alkylation of phenol may be carried out with alkylating agents of the types used to alkylate aromatic hydrocarbons in the manufacture of alkaryl sulphonates.
• Sulphurisation may be by reaction of the alkyl phenol with sulphur chloride or by reaction with sulphur. In the latter case, the alkyl phenol is usually present as the metal salt, although other sulphurisation promoters may be used, such as amines.
• Quaternary ammonium carboxylates are synthesised from:
• carboxylic acids are the simple monocarboxylic acids (such as formic acid and acetic acid), and the simple dicarboxylic acids (such as oxalic acid).
• quaternary ammonium salts which may be employed according to the present invention are commercially available. It is preferred to use one of those readily available compounds.
• the quaternary ammonium compounds can be synthesised in any suitable manner. Since the method of preparing the quaternary ammonium compounds is not part of the invention, the preparation of the compounds will not be described in detail. It should be noted, however, that we have two preferred methods for the synthesis of compounds such as quaternary ammonium sulphonates, sulphurised phenates and carboxylates.
• a quaternary ammonium hydroxide is prepared by reacting a quaternary ammonium halide (for example the chloride) with an alkali metal hydroxide (for example sodium hydroxide) in an alcohol (for example methanol).
• a quaternary ammonium halide for example the chloride
• an alkali metal hydroxide for example sodium hydroxide
• the rate of reaction may be increased by raising the reaction temperature above the ambient temperature. Once the reaction is complete the solvents and water are removed by distillation.
• the organic acid HA is reacted with a metal oxide or hydroxide to form the metal salt: HA + NaOH ---- ⁇ NaA + H2O
• the reaction is done in a suitable solvent (for example heptane or toluene) the water formed during the reaction may be removed by refluxing the solvent and using a Dean and Stark trap. Once all the water has been removed the solution of the metal salt is treated with a quaternary ammonium halide: NaA + [R4N] (+) Cl (-) ---- ⁇ [R4N] (+) A (-) + NaCl
• the metal halide is removed by filtration and the solvent is removed by distillation.
• the solvent can be removed by distillation and the metal halide filtered from the final product.
• the amount of quaternary ammonium salt which is added to the diesel fuel is a minor proportion by weight preferably less than 1 wt.% and most preferably 0.000001 to 0.1 wt.% especially 2 to 200 ppm.
• additive materials commonly used in diesel fuel may also be included in the diesel fuel compositions according to the present invention.
• Such other additive materials may comprise corrosion inhibitors, dyes and the like.
• the engine is run for 60 twenty minute cycles to simulate the urban driving cycle.
• Each cycle consists of four 5 minute periods as follows:
• the injectors were rated according to the test method of ISO 4010. This test works on the principle of a vacuum being maintained across the injector at a specific needle lift. In order to maintain this vacuum at the desired level the air-flow into the injector may vary. This air-flow into the injector is recorded. The air-flow into the injector becomes less as the injectors become coked. The results are recorded as the difference between clean and dirty, i.e. before and after tests air-flow.
• the formula used is as follows: In this and the following examples the results presented are the averages of four results at one specific setting of the injectors (0.1 mm lift).
• the diesel fuel used in Example 1 was a diesel fuel obtained from Italy.
• the compound according to the present invention tested in this diesel fuel was Compound A.
• a comparative test has been carried out using a typical product already being sold for injector nozzle cleanliness application (commercial product). This is an additive of the type described in the UK Patent Application No. 85-30907. It is a mixture of a phenol compound and a cyclic amide derived from a dicarboxylic acid or anhydride.
• the total duration of 20 hours represents 1,600 km (1,000 miles) of city driving conditions.
• Example 2 The tests in this example have been carried out as described for Example 2. Again, a UK commercial diesel fuel has been employed. A comparative result obtained with the commercial additive product mentioned in Example 1 is included in the attached Table III.

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

Priority Applications (1)

Applications Claiming Priority (2)

Publications (2)

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Family Applications (1)

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Cited By (37)

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Citations (10)

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• 1987
  • 1987-05-27 GB GB878712442A patent/GB8712442D0/en active Pending
• 1988
  • 1988-05-25 WO PCT/GB1988/000415 patent/WO1988009365A1/fr unknown
  • 1988-05-25 AU AU17945/88A patent/AU612153B2/en not_active Ceased
  • 1988-05-25 DE DE8888304753T patent/DE3866026D1/de not_active Expired - Lifetime
  • 1988-05-25 EP EP88304753A patent/EP0293192B1/fr not_active Expired - Lifetime
  • 1988-05-25 JP JP63504490A patent/JP2612926B2/ja not_active Expired - Lifetime
  • 1988-05-25 AT AT88304753T patent/ATE69258T1/de not_active IP Right Cessation
  • 1988-05-25 ES ES198888304753T patent/ES2026255T3/es not_active Expired - Lifetime
  • 1988-05-26 CA CA000567798A patent/CA1340601C/fr not_active Expired - Fee Related
• 1992
  • 1992-01-30 GR GR920400108T patent/GR3003682T3/el unknown

Patent Citations (10)

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