EP1054051A1 - Compositions de combustible diesel contenant des amines primaires d alkyle tertiaire - Google Patents

Compositions de combustible diesel contenant des amines primaires d alkyle tertiaire Download PDF

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Publication number
EP1054051A1
EP1054051A1 EP00303880A EP00303880A EP1054051A1 EP 1054051 A1 EP1054051 A1 EP 1054051A1 EP 00303880 A EP00303880 A EP 00303880A EP 00303880 A EP00303880 A EP 00303880A EP 1054051 A1 EP1054051 A1 EP 1054051A1
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EP
European Patent Office
Prior art keywords
fuel
tertiary alkyl
diesel fuel
primary amines
alkyl primary
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP00303880A
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German (de)
English (en)
Inventor
Rajiv Manohar Banavali
Bharati Dinkar Chheda
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Rohm and Haas Co
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Rohm and Haas Co
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Publication date
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Publication of EP1054051A1 publication Critical patent/EP1054051A1/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
    • C10L1/22—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
    • 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

Definitions

  • the present invention relates to diesel fuel additives and diesel fuel compositions containing such additives.
  • the present invention relates to a diesel fuel additive and diesel fuel compositions containing such additives which are useful as thermal stabilizers and in reducing deposits on injection nozzles of compression ignition diesel engines.
  • Diesel fuel is principally a blend of petroleum-derived fractions called middle distillates (heavier than gasoline, but lighter than lube oil) and may optionally contain additional additives useful for a variety of purposes.
  • oxidation inhibitors are added to reduce the formation of gums and insoluble residues that can clog fuel filters, and detergent-dispersant additives help keep fuel-insoluble materials in suspension and are therefore helpful in maintaining a clean engine and fuel delivery system.
  • Other additives include rust preventatives, anti-icing additives and cold-flow improvers. Ignition quality (cetane number) improvers are another type of common additive, and are added to increase the cetane number when the base fuel cetane does not meet requirements.
  • diesel fuel is injected into the compressed, high-temperature air in the combustion chamber, where it ignites spontaneously.
  • the most desirable fate of the carbon present in diesel fuels is to be emitted as carbon dioxide in the exhaust gas. If this is the case then the combustion is at its most efficient, which means that the maximum calorific value of the fuel is being exploited.
  • CO carbon monoxide
  • HC hydrocarbon
  • Particulates are of great concern as some studies are suggesting relationships between concentrations of fine particulates (less than 10 ⁇ in size) in urban air and human health problems, including asthma and heart disease.
  • Diesel fuel contains hydrocarbons having higher boiling point range than that of gasoline. Diesel fuel is designed to ignite spontaneously, quickly (within 1-2 milliseconds), and without a spark. The time lag between the initiation of injection and the initiation of combustion is known as ignition delay. In high speed diesel engines, a long ignition delay produces rough operation and knocking. To minimize ignition delay, it is necessary to maintain the fuel injector's ability to atomize a precise amount of fuel and mix it with available air. This in turn depends on the operation of the fuel injector. The performance of the fuel injector can be impaired by the build-up of deposits derived from the fuel. Thermal degradation of both fuel and crankcase lubricant components leads to the formation of deposits within fuel injectors. Deposit formation is worsened by hot combustion gases entering the nozzle. Deposits alter the close manufacturing tolerances of injectors and change fuel spray characteristics, leading to the observed degradation in engine performance.
  • IDI Indirect ignition
  • engines with pintle-type nozzles are the more sensitive to such deposits.
  • Engine symptoms resulting from IDI nozzle fouling are analogous to those caused by operation on fuel of inadequate cetane number. Increased noise, black smoke and exhaust emissions are all associated with severe IDI nozzle fouling, together with reduction in fuel economy.
  • Pintle-type nozzles are designed to release a restricted initial fuel, known as the pilot injection.
  • This pilot injection which occurs between needle lifts of 0 - 0.4 mm, initiates combustion ahead of the main fuel injection which occurs above 0.5 mm needle lift.
  • This smoother, progressive combustion is both more efficient and quieter than previous type diesel engines.
  • Deposits, which tend to form around the pintle tip, can strangulate the pilot injection by blocking the fuel flow. This results in a serious deviation from the designed combustion characteristics for the engine causing increases in noise and unburnt fuel exhaust emissions.
  • chemistries which are well known to bring detergency to the diesel fuel. All are based on molecules having: a polar portion, bringing the dispersancy effect; and a lipophilic (often a polymeric) portion, allowing the entire molecule to be soluble in fuel. Most important chemistries are polybutenylsuccinic amides or imides (especially those known as PIBSA derivatives).
  • Surfactant molecules frequently based on polymeric succinimide chemistry, help to control deposits within fuel injectors with significant benefits to engine performance.
  • Detergent additives are effective in preserving an acceptable pilot flow by preventing deposit build up and removing performed deposits. Measuring the performance of detergent additive formulations is an important aspect of developing a high performance diesel fuel. Different test engines and test procedures are employed in Europe and the USA; however, the common aim is to show benefits from the use of detergent additives compared with untreated base fuels, and thereby to allow the cost effective development of improved fuels.
  • the present invention is directed to a fuel additive composition effective to provide injector deposit inhibiting properties and thermal stability to diesel fuel, such composition consisting essentially of at least one tertiary alkyl primary amine.
  • the present invention is also directed to diesel fuel compositions conprising a major amount of diesel fuel and a minor amount of the fuel additive composition as discussed above.
  • (C 1 -C 21 ) means a straight chain, branched chain or cyclic groups having 1 to 21 carbon atoms per group.
  • the term “major amount” is understood to mean greater than 50 percent by weight, and the term “minor amount” is understood to mean less than 50 percent by weight.
  • TAPA means tertiary alkyl primary amine(s).
  • mL milliliters
  • L liters
  • mm millimeters
  • mg milligrams
  • g grams
  • rpm revolutions per minute. Unless otherwise specified, ranges specified are to be read as inclusive, references to percentages are by weight and all temperatures are in degrees centigrade (°C).
  • tertiary alkyl primary amines useful in the present invention are tertiary alkyl primary amines according to the formula: wherein:
  • C 1 -C 21 alkyl examples include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, octyl cyclooctyl, nonyl, cyclononyl, decyl, isodecyl, cyclodecyl, undecyl, dodecyl (also known as lauryl), tridecyl, tetradecyl (also known as myristyl), pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl
  • C 1 -C 21 alkenyl include, but are not limited to: ethenyl, n-propenyl, isopropenyl, 1-butenyl, cis-2-butenyl, isobutylene, trans-2-butenyl, 2-3, dimethyl-2-butenyl, 3-methyl-1-butenyl, 2-methyl-2-butene, 1-pentenyl, cis-2-pentenyl, trans-2-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl, 1-nonenyl, and 1-decenyl.
  • C 1 -C 21 substituted alkyl and alkenyl include, but are not limited to: the above recited alkyl and alkenyl groups substituted with hydroxy, halide such as fluorine, chlorine or bromine; cyano; alkoxy; haloalkyl; carbalkoxy; carboxy; amino; alkylamino derivatives and the like; or nitro groups.
  • Tertiary alkyl amines useful in the present invention include but are not limited to: 1,1,3,3-tetramethylbutylamine; an isomeric mixture of C 16 to C 22 tertiary alkyl primary amines; an isomeric mixture of C 10 to C 14 tertiary alkyl primary amines; an isomeric mixture of C 8 to C 10 tertiary alkyl primary amines; or mixtures thereof.
  • tertiary alkyl amine is an isomeric mixture of C 8 to C 10 and C 10 to C 14 tertiary alkyl primary amines.
  • the tertiary alkyl primary amine is an isomeric mixture of C 10 to C 14 tertiary alkyl primary amines.
  • Such tertiary alkyl primary amines are available from Rohm and Haas Company (Philadelphia, PA) under the PRIMENE® trademarks.
  • the tertiary alkyl primary amines of the present invention are present in diesel fuel compositions at a concentration of 1 to 2000 mg/L, preferably 10 to 800 mg/L, more preferably 20 to 600 mg/L and most preferably 40 to 500 mg/L.
  • the tertiary alkyl primary amines used in the diesel fuel compositions of the present invention are prepared using substrate compounds known as substrates for the Ritter reaction and include, for example, alcohols, alkenes, aldehydes, ketones, ethers. See, generally, L. I. Krimen and D. J. Cota, "The Ritter Reaction," Organic Reactions , 17(1969), pp. 213-325.
  • the process for preparing the amines is known in the art and is described, for instance, in US 5,527,949 and in co-pending provisional application 60/051,867.
  • the fuel additives of the present invention are also useful in maintaining or increasing the thermal stability of diesel fuels.
  • Diesel fuel is increasingly used as a circulating coolant for high pressure fuel injections systems.
  • the fuel In addition to its primary role as an energy source, the fuel also serves as the sole lubricant of critical moving parts and as a heat-transfer fluid.
  • Adequate thermal stability is a necessary requirement for the effective functioning of diesel fuel as a heat-transfer fluid. In modern heavy-duty diesel engines, only a portion of the fuel that is circulated to the fuel injectors is actually delivered to the combustion cylinders.
  • Fuels resistant to such thermal degradation must get a minimum 80% reflectance in the updated 150°C Accelerated Fuel Oil Stability Test (F21-61) at 180 minutes. Good thermal stability may become even more important in the future. Diesel engine manufacturers have indicated that engines under development to meet future exhaust emission standards will expose the fuel to more severe operating environments (stress), e.g., higher pressures and longer contact with high-temperature engine parts. the new premium diesel fuel specifications in USA will require a thermal stability and detergency pass test.
  • test engine is the most widely used light duty diesel engine in Europe, powering a substantial proportion of all vehicles in this class.
  • the Peugeot engine in common with many other IDI engines, employs a pintle type injector actuated by fuel pressure. Some of the main parameters of this test engine are provided below. Bore, mm 83.0
  • a metered quantity of fuel under pressure delivered by the pump, lifts the injector needle 30 from its seat.
  • the pintle type injector is normally closed by pressure from spring 20, thus preventing the flow of fuel.
  • a flow path is opened and a spray of small fuel droplets enters the combustion chamber.
  • Fuel pressure under injection is typically of the order of 100 bar.
  • Fuel samples A, B and C were, fresh test fuels without any additives and were obtained from commercial sources.
  • the fuel samples were analyzed to ensure conformance with specifications and stored under ambient temperature, in dark, and under nitrogen atmosphere. All tests were started within a month of obtaining the fresh samples. All commercial additives used were as received without further purification.
  • the C 9 , C 12 , and C 18 tertiary alkyl primary amines samples were commercial products sold by Rohm and Haas Company under the PRIMENE® trademark. The results are shown below in Table 1. Detailed Analysis of Test Fuel Samples Fuel # % Sulfur % Aromatics Cetane Number A 0.033 24.5 53.2 B 0.06 39 45 C 0.051 32 47
  • the engine In the mode tested, the engine typically undergoes severe nozzle coking on untreated base fuels. Flow loss at the onset of pilot fuel flow (0.1 mm needle lift) is typically 88-90% compared to the initial clean condition, after 6 hours test bed operation on an untreated base fuel.
  • the test procedure was as follows. A 50 mL sample of fuel oil in a test tube was placed in a 150 °C bath for 180 minutes. After removal from the bath the fuel was allowed to cool in air to 21 - 26 °C over a period of 90 minutes to 4 hours. The aged fuel was then filtered through 4.25 cm Whatman No 1 filter paper using vacuum filtration assembly. The paper was then washed with three portions, about 15 mL each, of iso-octane. The filter paper was dried under vacuum for one or two minutes. The filter paper was rated by measuring percent reflectance using a photovolt meter (model 577) using Search Unit Y with green filter. The filter paper was also rated for color by choosing a reference blotter which gave the best visual match.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
EP00303880A 1999-05-19 2000-05-09 Compositions de combustible diesel contenant des amines primaires d alkyle tertiaire Withdrawn EP1054051A1 (fr)

Applications Claiming Priority (2)

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US13490899P 1999-05-19 1999-05-19
US134908P 1999-05-19

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JP (1) JP2000345176A (fr)
CN (1) CN1274742A (fr)
CA (1) CA2307821A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG176084A1 (en) * 2009-05-15 2011-12-29 Lubrizol Corp Quaternary ammonium amide and/or ester salts

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3014793A (en) * 1956-02-28 1961-12-26 Exxon Research Engineering Co Distillate fuel oil compositions
US3998862A (en) * 1973-07-16 1976-12-21 Rohm And Haas Company Alkyl ammonium carboxylite salt-ethoxylated alkyl phenol esters
US4482355A (en) * 1983-12-30 1984-11-13 Ethyl Corporation Diesel fuel compositions
EP0698596A2 (fr) * 1994-08-23 1996-02-28 Rohm And Haas Company Procédé pour la préparation d'une amine et d'un ester d'alkyle
EP0890570A2 (fr) * 1997-07-07 1999-01-13 Rohm And Haas Company Amines primaires un alkyle tertiaire leur procédé de préparation
EP0947577A1 (fr) * 1998-03-09 1999-10-06 Rohm And Haas Company Compositions de combustible contenant des amines primaires avec un alkyle tertiaire

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3014793A (en) * 1956-02-28 1961-12-26 Exxon Research Engineering Co Distillate fuel oil compositions
US3998862A (en) * 1973-07-16 1976-12-21 Rohm And Haas Company Alkyl ammonium carboxylite salt-ethoxylated alkyl phenol esters
US4482355A (en) * 1983-12-30 1984-11-13 Ethyl Corporation Diesel fuel compositions
EP0698596A2 (fr) * 1994-08-23 1996-02-28 Rohm And Haas Company Procédé pour la préparation d'une amine et d'un ester d'alkyle
EP0890570A2 (fr) * 1997-07-07 1999-01-13 Rohm And Haas Company Amines primaires un alkyle tertiaire leur procédé de préparation
EP0947577A1 (fr) * 1998-03-09 1999-10-06 Rohm And Haas Company Compositions de combustible contenant des amines primaires avec un alkyle tertiaire

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CN1274742A (zh) 2000-11-29
CA2307821A1 (fr) 2000-11-19
JP2000345176A (ja) 2000-12-12

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