EP0147240B1 - Compositions de combustibles et des concentrés d'additifs, et leur utilisations pour inhiber la formation de dépôts - Google Patents

Compositions de combustibles et des concentrés d'additifs, et leur utilisations pour inhiber la formation de dépôts Download PDF

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EP0147240B1
EP0147240B1 EP84309143A EP84309143A EP0147240B1 EP 0147240 B1 EP0147240 B1 EP 0147240B1 EP 84309143 A EP84309143 A EP 84309143A EP 84309143 A EP84309143 A EP 84309143A EP 0147240 B1 EP0147240 B1 EP 0147240B1
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Prior art keywords
hydrocarbyl
fuel
composition
coking
amine
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EP0147240A2 (fr
EP0147240A3 (en
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John Vincent Hanlon
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Ethyl Corp
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Ethyl Corp
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Priority claimed from US06/567,071 external-priority patent/US4482355A/en
Priority claimed from US06/567,089 external-priority patent/US4482356A/en
Priority claimed from US06/567,090 external-priority patent/US4482357A/en
Priority to AT84309143T priority Critical patent/ATE41951T1/de
Priority to AT87201460T priority patent/ATE44042T1/de
Priority to AT87201461T priority patent/ATE43626T1/de
Priority to DE8484309143T priority patent/DE3477580D1/de
Application filed by Ethyl Corp filed Critical Ethyl Corp
Priority to DE8787201460T priority patent/DE3478695D1/de
Priority to DE8787201461T priority patent/DE3478466D1/de
Publication of EP0147240A2 publication Critical patent/EP0147240A2/fr
Publication of EP0147240A3 publication Critical patent/EP0147240A3/en
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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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/228—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles
    • C10L1/2283—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles containing one or more carbon to nitrogen double bonds, e.g. guanidine, hydrazone, semi-carbazone, azomethine
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
    • C10L1/231—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • 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

Definitions

  • the invention relates to compression ignition fuel compositions and additive mixtures of organic nitrate ignition accelerator and hydrocarbyl-substituted succinimide or succinamide, in amounts sufficient to resist the coking tendencies of compression ignition fuel compositions when used in the operation of indirect injection diesel engines.
  • Throttling diesel nozzles have recently come into widespread use in indirect injection automotive and light-duty diesel truck engines, i.e., compression ignition engines in which the fuel is injected into and ignited in a prechamber or swirl chamber. In this way, the flame front proceeds from the prechamber into the larger compression chamber where the combustion is completed. Engines designed in this manner allow for quieter and smoother operation.
  • the Figure of the Drawing illustrates the geometry of the typical throttling diesel nozzle (often referred to as the "pintle nozzle").
  • This invention provides distillate fuel for indirect injection compression ignition engines containing a combination of (a) organic nitrate ignition accelerator, and (b) hydrocarbyl-substituted succinimide or succinamide, and optionally:
  • the combination being present in an amount sufficient to suppress and preferably to minimize coking, especially throttling nozzle coking, in the prechambers or swirl chambers of indirect injection compression ignition engines operated on such fuel.
  • additive fluid concentrate for use in distillate fuels and which contains a combination defined above.
  • a still further embodiment of the present invention is a method of inhibiting coking, especially throttling nozzle coking, in the prechambers or swirl chambers of an indirect injection compression ignition engine, which comprises supplying said engine with a distillate fuel containing a combination as defined above, said combination being present in an amount sufficient to minimize such coking in an engine operated on such fuel.
  • a feature of this invention is that the combination of additives utilized in its practice is capable of suppressing coking tendencies of fuels used to operate indirect injection compression ignition engines. Such behavior was exhibited in a series of standard engine dynamometer tests conducted as described in Examples I, II and III hereinafter.
  • nitrate ignition accelerators component (a)
  • Preferred nitrate esters are the aliphatic or cycloaliphatic nitrates in which the aliphatic or cycloaliphatic group is saturated, contains up to about 12 carbons and, optionally, may be substituted with one or more oxygen atoms.
  • Typical organic nitrates that may be used are methyl nitrate, ethyl nitrate, propyl nitrate, isopropyl nitrate, allyl nitrate, butyl nitrate, isobutyl nitrate, sec-butyl nitrate, tert-butyl nitrate, amyl nitrate, isoamyl nitrate, 2-amyl nitrate, 3-amyl nitrate, hexyl nitrate, heptyl nitrate, 2-heptyl nitrate, octyl nitrate, isooctyl nitrate, 2-ethylhexyl nitrate, nonyl nitrate, decyl nitrate, undecyl nitrate, dodecyl nitrate, cyclopentyl nitrate, cyclohexyl
  • hydrocarbyl-substituted succinimides, component (b) of the fuels of this invention are well known. They are readily made by first reacting an olefinically unsaturated hydrocarbon of the desired molecular weight with maleic anhydride to form a hydrocarbyl-substituted succinic anhydride. Reaction temperatures of 100-250°C are used. With higher boiling olefinically-unsaturated hydrocarbons, good results are obtained at 200-250°C. This reaction can be promoted by the addition of chlorine.
  • Typical olefins include cracked wax olefins, linear alpha olefins, branched chain alpha olefins, polymers and copolymers of lower olefins. These include polymers of ethylene, propylene, isobutylene, 1-hexene, 1- decene and the like.
  • Useful copolymers are ethylene-propylene copolymers, ethylene-isobutylene copolymers, propylene-isobutylene copolymers, ethylene-1-decene copolymers and the like.
  • Hydrocarbyl substituents have also been made from olefin terpolymers.
  • Very useful products have been made from ethylene-C 3 - 12 alpha olefin - C S - 12 non-conjugated diene terpolymers; such as ethylene-propylene-1,4-hexadiene terpolymer; ethylene-propylene-1,5-cyclooctadiene terpolymer; ethylene-propylene-norbornene terpolymers and the like.
  • hydrocarbyl substituents are derived from butene polymers, especially polymers of isobutylene.
  • the molecular weight of the hydrocarbyl substituent can vary over a wide range. It is desirable that the hydrocarbyl group have a molecular weight of at least 500. Although there is no critical upper limit, a preferred range is 500-500,000 number average molecular weight. The more preferred average molecular weight is 700-5,000 and most preferably 900-3,000.
  • Hydrocarbyl-substituted succinimides and succinamides are made by reaction of the desired hydrocarbyl-substituted succinic anhydride with an amine having at least one reactive hydrogen atom bonded to an amine nitrogen atom.
  • amine having at least one reactive hydrogen atom bonded to an amine nitrogen atom.
  • examples of these are methyl amine, dimethyl amine, n-butyl amine, di-(n-dodecyl) amine, N-(aminoethyl) piperidine, piperazine, N-(3-aminopropyl) piperazine, and the like.
  • the amine has at least one reactive primary amine group capable of reacting to form the preferred succinimides.
  • primary amines are n-octyl amine, N,N-dimethyl-1,3-propane diamine, N-(3-aminopropyl) piperazine, 1,6-hexane diamine, and the like.
  • Hydroxyalkyl amines can also be used to make the succinimide-succinamide components of the invention which contain some ester groups. These amines include ethanol amine, diethanol amine, 2-hydroxypropyl amine, N-hydroxyethyl ethylenediamine and the like. Such hydroxyalkyl amines can be made by reacting a lower alkylene oxide, such as ethylene oxide, propylene oxide or butylene oxide with ammonia or a primary or secondary amine such as ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylenepentamine and the like.
  • a lower alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide
  • ammonia or a primary or secondary amine such as ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylenepentamine and the like.
  • a more preferred class of primary amines used to make the succinimide, succinamide or mixtures thereof are the polyalkylene amines. These are polyamines and mixtures of polyamines which have the general formula wherein R is a divalent aliphatic hydrocarbon group having 2-4 carbon atoms and n is an integer from 1-10 including mixtures of such polyalkylene amines.
  • the polyalkylene amine is a polyethyleneamine containing 2-6 ethyleneamine units. These are represented by the above formula in which R is the group ⁇ CHCH ⁇ and n has a value of 2-6.
  • the amine used to make the succinimide, succinamide or mixture thereof need not be all amine.
  • a mono or poly-hydroxyalcohol may be included in the reaction.
  • Such alcohols can be reacted concurrently with the amine or the two alcohol and amine may be reacted sequentially.
  • Useful alcohols are methanol, ethanol, n-dodecanol, 2-ethyl hexanol, ethylene glycol, propylene glycol, diethylene glycol, 2-ethoxy ethanol, trimethylol propane pentaerythritol, dipentaerythritol and the like.
  • the reaction between the hydrocarbyl-substituted succinic anhydride and the amine can be carried out by mixing the components and heating the mixture to a temperature high enough to cause a reaction to occur but not so high as to cause decomposition of the reactants or products or the anhydride may be heated to reaction temperature and the amine added over an extended period.
  • a useful temperature is 100-250°C. Best results are obtained by conducting the reaction at a temperature high enough to distill out water formed in the reaction.
  • a preferred succinimide-succinamide component is available as an article of commerce from the Edwin Cooper Company under the designation HITEC O E-644.
  • This product comprises a mixture of active ingredients and solvent.
  • the product as received should be used at a concentration of at least about 40 PTB (pounds per thousand barrels) - 0.11436 grams per liter - to insure that the finished blend contains an adequate quantity of the foregoing succinimide-succinamide ingredient although smaller amounts may be successfully employed.
  • the nitrate ignition accelerator-component (a) - should be present in an amount of at least 100 to 1000 PTB (pounds per thousand barrels) - 0.2859 to 2.859 grams per liter - of the base fuel.
  • the concentration of the ignition accelerator is 400 to 600 PTB (1.1436 to 1.7154 grams per liter).
  • the coking-inhibiting components (a) and (b) of the invention can be added to the fuels by any means known in the art for incorporating small quantities of additives into distillate fuels.
  • Components (a) and (b) can be added separately or they can be combined and added together. It is convenient to utilize additive fluid mixtures which consist of organic nitrate ignition accelerator and hydrocarbyl-substituted succinimide-succinamide agents. These additive fluid mixtures are added to distillateJuels.
  • part of the present invention are coking inhibiting fluids which comprise organic nitrate ignition accelerator and hydrocarbyl-substituted succinimide-succinamide.
  • Such fluids in addition to resulting in great convenience in storage, handling, transportation, blending with fuels, and so forth, also are potent concentrates which serve the function of inhibiting or minimizing the coking characteristics of compression ignition distillate fuels used to operate indirect compression ignition engines.
  • the amount of components (a) and (b) can vary widely.
  • the fluid compositions contain 5 to 95% by weight of the organic nitrate ignition accelerator component and 5 to 95% by weight of the hydrocarbyl-substituted succinimide-succinamide component.
  • a preferred distillate fuel composition contains from 0.1 to 0.5% by weight of the combination containing from 25% to 95% by weight of the organic nitrate ignition accelerator and from 75% to 5% by weight of the hydrocarbyl-substituted succinimide-succinamide component.
  • the additive fluids, as well as the distillate fuel compositions of the present invention may also contain other additives such as, corrosion inhibitors, antioxidants, metal deactivators, detergents, cold flow improvers, inert solvents or diluents, and the like.
  • a more preferred distillate fuel composition includes a hydrocarbyl amine in combination with the present additives.
  • hydrocarbyl amines While a variety of hydrocarbyl amines may be used in the fuel compositions of this invention, a primary aliphatic amine, the aliphatic group of which is tertiary, e.g., an amine of the formula: wherein R is one or a mixture of tertiary aliphatic groups containing 8 to 18 or more (preferably 12-16) carbon atoms is preferred. Most preferably, these tertiary aliphatic groups are tertiary alkyl groups. It is also preferred that hydrocarbyl amine component (c) include in addition to the above-depicted amine one or more hydrocarbyl amines differing therefrom.
  • U.S. Pat. No. 3,909,215 gives a description of the various hydrocarbyl amines having from 3 to 60 carbons and from 1 to 10 nitrogens which may be employed in the fuels of this invention.
  • a few additional examples of desirable amines include 2,6-di-tert-butyl-a-dimethylamino-p-cresol, N-cyclohexyl-N,N-dimethylamine, and N-alkyl-N,N-dimethylamines in which the alkyl group is one or a combination of alkyl groups preferably having 8 to 18 or more carbon atoms.
  • a particularly preferred hydrocarbyl amine is available commercially from the Rohm and Haas Company under the designation Primene 81 R.
  • the Primene 81 R is believed to be a mixture of primary aliphatic amines in which the aliphatic groups are predominantly C 12 and C 14 tertiary alkyl groups.
  • the fuels of this invention should contain at least 1.5 to 40 PTB (0.00429 to 0.1143 grams/liter of component (c), the hydrocarbyl amine.
  • another embodiment of the present invention is distillate fuel for indirect injection compression ignition engines containing a combination of (a) organic nitrate ignition accelerator, (b) hydrocarbyl-substituted succinimide, and (c) hydrocarbyl amine, said combination being present in an amount sufficient to minimize coking, especially throttling nozzle coking in the prechambers or swirl chambers in indirect injection compression ignition engines operated on such fuel.
  • distillate fuel additive concentrate comprising the combination of (a), (b) and (c).
  • these additive fuel concentrates will contain as much as 50% by weight of the combination of organic nitrate ignition accelerator and hydrocarbyl-substituted succinimide and up to 50% of the hydrocarbyl amine or other additives when they are present.
  • a method of inhibiting coking, especially throttling nozzle coking in the prechambers or swirl chambers of an indirect injection compression ignition engine which comprises supplying said engine with a distillate fuel containing a combination of (a) organic nitrate ignition accelerator, (b) hydrocarbyl-substituted succinimide or succinamide and (c) hydrocarbyl amine, said combination being present in an amount sufficient to suppress and preferably to minimize such coking in an engine operated on such fuel.
  • Another additive which can be used to advantage in the present invention is the metal deactivator N,N'-disalicylidene-1,2-diaminopropane.
  • This compound 80 weight percent active in 20 weight percent toluene solvent
  • Ethyl MDA.
  • the fuels of this invention should contain at least 0.2 to 5 PTB (0.00572 to 0.012 grams per liter) of component (d), N,N'-disalicylidene-1,2-diaminopropane.
  • another embodiment of the present invention is distillate fuel for indirect injection compression ignition engines containing a combination of (a) organic nitrate ignition accelerator, (b) hydrocarbyl-substituted succinimide or succinamide, (c) hydrocarbyl amine, and (d) N,N'-disalicylidene-1,2-diaminopropane, said combination being present in an amount sufficient to suppress and preferably to minimize coking, especially throttling nozzle coking in the prechambers or swirl chambers in indirect injection compression ignition engines operated on such fuel.
  • distillate fuel additive concentrate comprising the combination of (a), (b), (c) and (d).
  • these additive fuel compositions will contain as much as 50% by weight of the combination of organic nitrate ignition accelerator and hydocarbyl-substituted succinimide-succinamide and up to 50% of the combination of hydrocarbyl amine and N,N'-disalicylidene-1,2-diaminopropane or other additives when they are present.
  • a method of inhibiting coking, especially throttling nozzle coking in the prechambers or swirl chambers in an indirect injection compression ignition engine which comprises supplying said engine with a distillate fuel containing a combination of (a) organic nitrate ignition accelerator, (b) hydrocarbyl-substituted succinimide or succinamide, (c) hydrocarbyl amine and (d) N,N'-disalicylidene-1,2-diaminopropane, said combination being present in an amount to suppress and preferably to minimize such coking in an engine operated on such fuel.
  • the base fuel employed in these engine tests was a commercially-available diesel fuel having a nominal cetane rating of 42.
  • FIA analysis indicated the fuel was composed by volume of 31.5% aromatics, 3.0% olefins and 65.5% saturates.
  • Its distillation range (ASTM D-158) was as follows:
  • Other inspection data on the base fuel were as follows:
  • Fuel A contained a combination of (i) 506 PTB (1.447 grams/liter) of mixed octyl nitrates (a commercial product available from Ethyl Corporation under the designation DII-3 Ignition Improver), (ii) 41 PTB (0.117 gram/liter) of HITEC O E-644, a product of Edwin Cooper, Inc., believed to be a hydrocarbyl succinimide-succinamide made by reacting two moles of a polyisobutenyl succinic anhydride (PIBSA) with one mole of a polyethylene amine mixture having an average composition corresponding to tetraethylene pentamine, (iii) 14 PTB (0.04 grams/liter) of a hydrocarbyl amine available commercially from Rohm and Haas Company under the designation Primene 81 R and (iv) 1.7 PTB (0.00486 grams/liter) of "Ethyl" Metal Deactivator
  • PIBSA polyisobutenyl succin
  • the Primene 81R is believed to be a mixture of primary aliphatic amines in which the aliphatic groups are predominantly C 12 and C 14 tertiary alkyl groups.
  • Shell Rotella T an SAE 30, SF/CD oil was used as the crankcase lubricant.
  • new Bosch DNOSD - 1510 nozzles were installed using new copper gaskets and flame rings.
  • the fuel line was flushed with the new test fuel composition to be tested and the fuel filter bowl and fuel return reservoir were emptied to avoid additive carry-over from test-to-test.
  • the engine was operated at 1000 rpm, light load for 15 minutes. After this warm-up, the engine was subjected to the following automatic cycle: The above 20-minute cycle was repeated 60 times and the test was completed by running the engine at idle for another 30 minutes. The total elapsed time was thus 20.5 hours per test.
  • Hydrocarbon exhaust emissions were measured at the start of each test (after the first 20-minute cycle), at the 6-hour test interval and at the end of the test. These measurements were made at 750, 1000, and 1400 rpm idle. Noise level readings were made at a location three feet from the engine exhaust side. The measurements were made at the start and at the end of the test while operating at three idle speds, viz., 750, 1000 and 1400 rpm.

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Claims (10)

1. Composition de combustible distillé pour moteurs à allumage par compression à injection indirecte, contenant, en quantité suffisante pour supprimer et de préférence pour minimiser le dépôt de coke dans les injecteurs de moteurs à allumage par compression à injection indirecte fonctionnant avec un tel combustible, un mélange formé (a) d'un accélérateur d'allumage du type d'un nitrate organique et (b) d'un succinimide ou succinamide à substituant hydrocarbyle et, à titre facultatif:
(c) une hydrocarbylamine de 3 à 60 atomes de carbone et 1 à 10 atomes d'azote, ou bien
une association de l'hydrocarbylamine (c) et (d) de N,N'-disalicylidène-1,2-diaminopropane.
2. Composition suivant la revendication 1, dans laquelle l'accélérateur d'allumage est un mélange de nitrates d'octyle.
3. Composition suivant la revendication 1 ou la revendication 2, dans laquelle le succinimide à substituant hydrocarbyle est un succinimide substitué par un polymère oléfinique, dont ledit substituant polymérique oléfinique a un poids moléculaire moyen de 500 à 500 000.
4. Composition suivant la revendication 3, dans laquelle le substituant polymérique oléfinique est un substituant polyisobutène ayant un poids moléculaire moyen de 700 à 5000.
5. Composition suivant la revendication 3 ou la revendication 4, dans laquelle la portion succinimide est dérivée d'une polyalkylène-amine répondant à la formule
Figure imgb0014
dans laquelle R est un groupe hydrocarboné aliphatique divalent de 2 à 4 atomes de carbone et n est un nombre entier de 1 à 10, y compris des mélanges desdites polyalkylène-amines.
6. Composition suivant la revendication 5, dans laquelle la polyalkylène-amine est une polyéthylène- amine ayant 2 à 6 motifs éthylène-amine.
7. Composition suivant l'une quelconque des revendications 1 à 6, contenant, en une quantité suffisante pour supprimer et de préférence pour minimiser le dépôt de coke sur les injecteurs de moteurs à allumage par compression à injection indirecte fonctionnant avec un tel combustible, au moins l'association formée entre (a) un accélérateur d'allumage du type d'un nitrate organique, (b) un succinimide ou succinamide à substituant hydrocarbyle et (c) une hydrocarbylamine ayant 3 à 60 atomes de carbone et 1 à 10 atomes d'azote.
8. Composition suivant la revendication 7, contenant également (d) du N,N'-disalicylidène-1,2-diaminopropane.
9. Concentré liquide d'additif destiné à être utilisé dans des combustibles distillés, qui contient une association définie dans l'une quelconque des revendications 1 à 8.
10. Procédé pour inhiber le dépôt de coke sur les injecteurs d'un moteur à allumage par compression à injection indirecte pendant son fonctionnement, procédé qui consiste à alimenter ledit moteur avec une composition de combustible distillé contenant en une quantité suffisante pour supprimer et de préférence pour minimiser ce depôt de coke dans le moteur utilisant ce combustible, une association définie suivant l'une quelconque des revendications 1 à 8.
EP84309143A 1983-12-30 1984-12-28 Compositions de combustibles et des concentrés d'additifs, et leur utilisations pour inhiber la formation de dépôts Expired EP0147240B1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DE8787201461T DE3478466D1 (en) 1983-12-30 1984-12-28 Fuel composition and additive concentrates, and their use in inhibiting engine coking
DE8787201460T DE3478695D1 (en) 1983-12-30 1984-12-28 Fuel composition and additive concentrates, and their use in inhibiting engine coking
AT84309143T ATE41951T1 (de) 1983-12-30 1984-12-28 Brennstoffzusammensetzungen und zusatzkonzentrate und ihre verwendung zur schlamminhibition.
AT87201460T ATE44042T1 (de) 1983-12-30 1984-12-28 Brennstoffzusammensetzung und zusatzkonzentrate und ihren verwendung zur motorschlamminhibierung.
AT87201461T ATE43626T1 (de) 1983-12-30 1984-12-28 Brennstoffzusammensetzung und zusatzkonzentrate und deren verwendung zur motorschlamminhibierung.
DE8484309143T DE3477580D1 (en) 1983-12-30 1984-12-28 Fuel compositions and additive concentrates, and their use in inhibiting engine coking

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US567090 1983-12-30
US567089 1983-12-30
US06/567,071 US4482355A (en) 1983-12-30 1983-12-30 Diesel fuel compositions
US567071 1983-12-30
US06/567,090 US4482357A (en) 1983-12-30 1983-12-30 Fuel Compositions
US06/567,089 US4482356A (en) 1983-12-30 1983-12-30 Diesel fuel containing alkenyl succinimide

Related Child Applications (2)

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EP87201461.8 Division-Into 1984-12-28
EP87201460.0 Division-Into 1984-12-28

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EP0147240A2 EP0147240A2 (fr) 1985-07-03
EP0147240A3 EP0147240A3 (en) 1986-04-02
EP0147240B1 true EP0147240B1 (fr) 1989-04-05

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EP87201460A Expired EP0247706B1 (fr) 1983-12-30 1984-12-28 Composition de combustible et concentrés d'additifs et leurs utilisations pour inhiber la formation de dépôts dans un moteur
EP84309143A Expired EP0147240B1 (fr) 1983-12-30 1984-12-28 Compositions de combustibles et des concentrés d'additifs, et leur utilisations pour inhiber la formation de dépôts

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EP87201460A Expired EP0247706B1 (fr) 1983-12-30 1984-12-28 Composition de combustible et concentrés d'additifs et leurs utilisations pour inhiber la formation de dépôts dans un moteur

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CA (3) CA1270642A (fr)

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Also Published As

Publication number Publication date
CA1270642A (fr) 1990-06-26
EP0247706A2 (fr) 1987-12-02
EP0247706B1 (fr) 1989-06-14
EP0251419B1 (fr) 1989-05-31
EP0251419A1 (fr) 1988-01-07
EP0147240A2 (fr) 1985-07-03
EP0247706A3 (en) 1988-01-13
CA1284883C (fr) 1991-06-18
EP0147240A3 (en) 1986-04-02
CA1284583C (fr) 1991-06-04

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