EP0247706A2 - Fuel composition and additive concentrates, and their use in inhibiting engine coking - Google Patents
Fuel composition and additive concentrates, and their use in inhibiting engine coking Download PDFInfo
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- EP0247706A2 EP0247706A2 EP87201460A EP87201460A EP0247706A2 EP 0247706 A2 EP0247706 A2 EP 0247706A2 EP 87201460 A EP87201460 A EP 87201460A EP 87201460 A EP87201460 A EP 87201460A EP 0247706 A2 EP0247706 A2 EP 0247706A2
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- Prior art keywords
- composition
- fuel
- coking
- nitrate
- engine
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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
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- 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, 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
-
- 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
-
- 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
- C10L1/22—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, 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
- C10L1/23—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, 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
- C10L1/234—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)
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- 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, hydrocarbyl amine and N,N ⁇ -disalicylidene-1,2-diaminopropane, 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 refered to as the "pintle nozzle").
- the carbon tends to fill in all of the available corners and surfaces of the obturator 10 and the form 12 until a smooth profile is achieved.
- the carbon also tends to block the drilled orifice 14 in the injector body 16 and fill up to the seat 18.
- carbon builds up on the form 12 and the obturator 10 to such an extent that it interferes with the spray pattern of the fuel issuing from around the perimeter of orifice 14.
- Such carbon build up or coking often results in such undesirable consequences as delayed fuel injection, increased rate of fuel injection, increased rate of combustion chamber pressure rise, and increased engine noise, and can also result in an excessive increase in emission from the engine of unburned hydrocarbons.
- This invention provides distillate fuel for indirect injection compression ignition engines containing a combination of (a) organic nitrate ignition accelerator, (b) hydrocarbyl amine having from 3 to 60 carbons and from 1 to 10 nitrogens and (c) N,N-disalicylidene-1,2-diaminopropane, 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 as 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 suppress and preferably 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 the Example 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, cyclohexy
- 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).
- hydrocarbyl amines (b) 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: R-NH2 wherein R is one or a mixture of tertiary aliphatic groups containing 8 to 18 or more (preferably 12-16) carbon atoms is preferred.
- R-NH2 an amine of the formula: R-NH2 wherein R is one or a mixture of tertiary aliphatic groups containing 8 to 18 or more (preferably 12-16) carbon atoms
- these tertiary aliphatic groups are tertiary alkyl groups.
- hydrocarbyl amine component (b) 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- ⁇ -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 81R.
- the Primene 81R is believed to be a mixture of primary aliphatic amines in which the aliphatic groups are predominantly C12 and C14 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 (b), the hydrocarbyl amine.
- the metal deactivator N,N ⁇ -disalicylidene-1,2-diaminopropane (d) is also included in the combination.
- This compound 80 weight percent active compound in 20 weight percent toluene solvent
- Ethyl is available as an article of commerce from Ethyl Corporation under the designation "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 (c), the metal deactivator, preferably N,N ⁇ -disalicylidene-1,2-diaminopropane.
- the amount of components (a), (b) and (c) can vary widely.
- the fluid compositions contain 10 to 97.9% by weight of the organic nitrate ignition accelerator component, 2.0 to 75% by weight of the hydrocarbyl amine and 0.1 to 15% by weight metal deactivator.
- from 0.01% by weight up to 1.0% by weight of the combination of the components (a), (b) and (c) will be sufficient to provide good coking-inhibiting properties to the distillate fuel.
- a preferred distillate fuel composition contains from 0.1 to 0.5% by weight of the combination containing from 50 to 97.9% by weight of the organic nitrate ignition accelerator, from 2.0 to 45% by weight of the hydrocarbyl amine and from 0.1 to 5.0% by weight of the metal deactivator component.
- 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 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.
- 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:
- test blend was prepared from this base fuel.
- the test fuel contained a combination of (i) 506 PTB (1.447 grams per liter) of mixed octyl nitrates (a commercial product available from Ethyl Corporation under the designation DII-3 Ignition Improver), (ii) 13.2 PTB (0.0377 grams per liter) of a hydrocarbyl amine available commercially from Rohm and Haas Company under the designation Primene 81R and (iii) 1.7 PTB (0.00486 grams per liter) of "Ethyl" Metal Deactivator, a product of Ethyl Corporation, the active ingredient of which is N,N ⁇ -disalicylidene-1,2-diaminopropane.
- the Primene 81R is believed to be a mixture of primary aliphatic amines in which the aliphatic groups are predominantly C2 and C14 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 speeds, viz., 750, 1000 and 1400 rpm.
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Abstract
- (a) organic nitrate ignition accelerator,
- (b) hydrocarbyl amine having from 3 to 60 carbons and from 1 to 10 nitrogens, and
- (c) N,Nʹ-disalicylidene-1,2-diaminopropane.
Description
- The invention relates to compression ignition fuel compositions and additive mixtures of organic nitrate ignition accelerator, hydrocarbyl amine and N,Nʹ-disalicylidene-1,2-diaminopropane, 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 refered to as the "pintle nozzle").
- Unfortunately, the advent of such engines has given rise to a new problem, that of excessive coking on the critical surfaces of the injectors that inject fuel into the prechamber or swirl chamber of the engine. In particular, and with reference to the accompanying Figure, the carbon tends to fill in all of the available corners and surfaces of the obturator 10 and the
form 12 until a smooth profile is achieved. The carbon also tends to block the drilledorifice 14 in theinjector body 16 and fill up to theseat 18. In severe cases, carbon builds up on theform 12 and the obturator 10 to such an extent that it interferes with the spray pattern of the fuel issuing from around the perimeter oforifice 14. Such carbon build up or coking often results in such undesirable consequences as delayed fuel injection, increased rate of fuel injection, increased rate of combustion chamber pressure rise, and increased engine noise, and can also result in an excessive increase in emission from the engine of unburned hydrocarbons. - While low fuel cetane number is believed to be a major contributing factor to the coking problem, it is not the only relevant factor. Thermal and oxidative stability (lacquering tendencies), fuel aromaticity, and such fuel characteristics as viscosity, surface tension and relative density have also been indicated to play a role in the coking problem.
- An important contribution to the art would be a fuel composition which has enhanced resistance to coking tendencies when employed in the operation of indirect injection diesel engines.
- This invention provides distillate fuel for indirect injection compression ignition engines containing a combination of (a) organic nitrate ignition accelerator, (b) hydrocarbyl amine having from 3 to 60 carbons and from 1 to 10 nitrogens and (c) N,N-disalicylidene-1,2-diaminopropane, 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.
- Included in the invention is additive fluid concentrate for use in distillate fuels and which contains a combination as defined above.
- Since the invention also embodies the operation of an indirect injection compression ignition engine in a manner which results in reduced coking, 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 suppress and preferably 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 the Example hereinafter.
- A wide variety of organic nitrate ignition accelerators, component (a), may be employed in the fuels of this invention. 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 nitrate, methylcyclohexyl nitrate, cyclododecyl nitrate, 2-ethyoxyethyl nitrate, 2-(2-ethoxy-ethoxy)ethyl nitrate, tetra-hydrofuranyl nitrate, and the like. Mixtures of such materials may also be used. The preferred ignition accelerator for use in the fuels of this invention is a mixture of octyl nitrates available as an article of commerce from Ethyl Corporation under the designation DII-3 ignition improver.
- 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. Preferably, the concentration of the ignition accelerator is 400 to 600 PTB (1.1436 to 1.7154 grams per liter).
- It is not believed that there is anything critical as regards the maximum amount of component (a) used in the fuel. Thus, the maximum amount of this component will probably be governed in any given situation by matters of choice and economics.
- While a variety of hydrocarbyl amines (b) 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:
R-NH₂
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 (b) 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-α-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 81R. The Primene 81R is believed to be a mixture of primary aliphatic amines in which the aliphatic groups are predominantly C₁₂ and C₁₄ 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 (b), the hydrocarbyl amine.
- The metal deactivator N,Nʹ-disalicylidene-1,2-diaminopropane (d) is also included in the combination. This compound (80 weight percent active compound in 20 weight percent toluene solvent) is available as an article of commerce from Ethyl Corporation under the designation "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 (c), the metal deactivator, preferably N,Nʹ-disalicylidene-1,2-diaminopropane.
- In these fluid compositions, the amount of components (a), (b) and (c) can vary widely. In general, the fluid compositions contain 10 to 97.9% by weight of the organic nitrate ignition accelerator component, 2.0 to 75% by weight of the hydrocarbyl amine and 0.1 to 15% by weight metal deactivator. Typically, from 0.01% by weight up to 1.0% by weight of the combination of the components (a), (b) and (c) will be sufficient to provide good coking-inhibiting properties to the distillate fuel. A preferred distillate fuel composition contains from 0.1 to 0.5% by weight of the combination containing from 50 to 97.9% by weight of the organic nitrate ignition accelerator, from 2.0 to 45% by weight of the hydrocarbyl amine and from 0.1 to 5.0% by weight of the metal deactivator component.
- 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 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.
- The practice and advantages of this invention will become still further apparent from the following illustrative Example.
- In order to determine the effect of the fuel compositions of the present invention on the coking tendency of diesel injectors in indirect injection compression ignition engines, use was made of a commercial diesel engine operated on a coking test cycle developed by Institute Francais Petrole and as practiced by Peugeot S. A. The amount of coking together with a quantitative indication of the adverse consequences of such coking was determined by means of (i) injector air flow performance, (ii) emission of unburned hydrocarbons, (iii) engine noise, and (iv) injector deposit ratings. The engine employed in the tests was a 1982 Peugeot 2.3 liter, 4-cylinder, turbo-charged XD2S diesel engine connected to a Midwest dynamometer through an engine clutch. This engine is equipped with Bosch injectors positioned within prechambers, and is deemed representative of the indirect injection compression ignition engines widely used in automobiles and light-duty trucks.
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- Other inspection data on the base fuel were as follows:
Kinematic Viscosity, (ASTM D-445) . . . 3.50 Centistokes, 40°C
Pour Point (ASTM D-97) . . . . . . . . .-26°C
Cloud Point (ASTM D-97) . . . . . . . . 33°C
Flash Point (ASTM D-93) . . . . . . . . 91°C
Steam Jet Gum . . . . . . . . . . . . . 2.4 mg/100 ml
Aniline Point (ASTM D-611) . . . . . . . 143.4°F (61.89°C)
Total Sulfur. . . . . . . . . . . . . . 0.41 wt. %
Ramsbottom Carbon, % (ASTM D-524) . . . 0.1460 on 10%
Residuum
Gravity (ASTM D-287) . . . . . . . . . . 31.8 °API
Specific Gravity @ 25°C . . . . . . . . 0.86
Cetane rating . . . . . . . . . . . . . 41 - A test blend was prepared from this base fuel. The test fuel contained a combination of
(i) 506 PTB (1.447 grams per liter) of mixed octyl nitrates (a commercial product available from Ethyl Corporation under the designation DII-3 Ignition Improver), (ii) 13.2 PTB (0.0377 grams per liter) of a hydrocarbyl amine available commercially from Rohm and Haas Company under the designation Primene 81R and (iii) 1.7 PTB (0.00486 grams per liter) of "Ethyl" Metal Deactivator, a product of Ethyl Corporation, the active ingredient of which is N,Nʹ-disalicylidene-1,2-diaminopropane. - The Primene 81R is believed to be a mixture of primary aliphatic amines in which the aliphatic groups are predominantly C₂ and C₁₄ tertiary alkyl groups.
- The manufacturer gives the following typical properties for its "Ethyl" metal Deactivator:
Form Liquid
Color Amber
Density, at 68°F
g/ml 1.0672
lb/gal 8.91
Active ingredient, wt % 80
Solvent vehicle (toluene), wt % 20
Flash point, open cup, °F 84 (28.89°C)
Fire point, °F 100 (37.78°C)
Solubility
In gasoline (Typical) Saturate solution contains 94% MDA
In water, wt. % 0.04 - Shell Rotella T, an SAE 30, SF/CD oil was used as the crankcase lubricant.
- Before starting each test, 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.
- At the start of each 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:
-
- 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 speeds, viz., 750, 1000 and 1400 rpm.
- After the test operation, the injectors were carefully removed from the engine so as not to disturb the deposits formed thereon. Measurements were made of air flow through each nozzle at different pintle lifts, and pintle deposits were rated using the CRC deposit rating system.
-
- The results presented in the Table show that there were less coking deposits (higher air flow rate and fewer deposits), less engine noise and less hydrocarbon emissions with the fuel of the invention, as compared to the Base Fuel.
Claims (10)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT87201460T ATE44042T1 (en) | 1983-12-30 | 1984-12-28 | FUEL COMPOSITION AND ADDITIVE CONCENTRATES AND THEIR USE FOR ENGINE SLUDGE INHIBITION. |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US567090 | 1983-12-30 | ||
US06/567,090 US4482357A (en) | 1983-12-30 | 1983-12-30 | Fuel Compositions |
US567089 | 1983-12-30 | ||
US06/567,071 US4482355A (en) | 1983-12-30 | 1983-12-30 | Diesel fuel compositions |
US567071 | 1983-12-30 | ||
US06/567,089 US4482356A (en) | 1983-12-30 | 1983-12-30 | Diesel fuel containing alkenyl succinimide |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84309143.0 Division | 1984-12-28 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0247706A2 true EP0247706A2 (en) | 1987-12-02 |
EP0247706A3 EP0247706A3 (en) | 1988-01-13 |
EP0247706B1 EP0247706B1 (en) | 1989-06-14 |
Family
ID=27416008
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87201461A Expired EP0251419B1 (en) | 1983-12-30 | 1984-12-28 | Fuel composition and additive concentrates, and their use in inhibiting engine coking |
EP87201460A Expired EP0247706B1 (en) | 1983-12-30 | 1984-12-28 | Fuel composition and additive concentrates, and their use in inhibiting engine coking |
EP84309143A Expired EP0147240B1 (en) | 1983-12-30 | 1984-12-28 | Fuel compositions and additive concentrates, and their use in inhibiting engine coking |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87201461A Expired EP0251419B1 (en) | 1983-12-30 | 1984-12-28 | Fuel composition and additive concentrates, and their use in inhibiting engine coking |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84309143A Expired EP0147240B1 (en) | 1983-12-30 | 1984-12-28 | Fuel compositions and additive concentrates, and their use in inhibiting engine coking |
Country Status (2)
Country | Link |
---|---|
EP (3) | EP0251419B1 (en) |
CA (3) | CA1270642A (en) |
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EP1305380A1 (en) * | 2000-07-28 | 2003-05-02 | Magnum Environmental Technologies Inc. | Improved fuel additive formulation and method of using same |
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WO2017203003A1 (en) * | 2016-05-26 | 2017-11-30 | Shell Internationale Research Maatschappij B.V. | Fuel compositions |
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US5340488A (en) * | 1989-11-15 | 1994-08-23 | Petro Chemical Products, Inc. | Composition for cleaning an internal combustion engine |
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- 1984-12-28 EP EP87201460A patent/EP0247706B1/en not_active Expired
- 1984-12-28 EP EP84309143A patent/EP0147240B1/en not_active Expired
-
1990
- 1990-01-19 CA CA000615608A patent/CA1284583C/en not_active Expired - Fee Related
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WO1991016408A1 (en) * | 1990-04-12 | 1991-10-31 | Exxon Chemical Limited | Fuel oil compositions |
EP1305380A1 (en) * | 2000-07-28 | 2003-05-02 | Magnum Environmental Technologies Inc. | Improved fuel additive formulation and method of using same |
EP1305380A4 (en) * | 2000-07-28 | 2004-12-15 | Magnum Environmental Technolog | Improved fuel additive formulation and method of using same |
US7491249B2 (en) | 2000-07-28 | 2009-02-17 | Mazoil Technologies, Ltd. | Fuel additive formulation and method of using same |
AU2010200065B2 (en) * | 2000-07-28 | 2013-03-07 | Mazoil Technologies Limited | Improved fuel additive formulation and method of using same |
WO2017203003A1 (en) * | 2016-05-26 | 2017-11-30 | Shell Internationale Research Maatschappij B.V. | Fuel compositions |
Also Published As
Publication number | Publication date |
---|---|
EP0147240A2 (en) | 1985-07-03 |
CA1270642A (en) | 1990-06-26 |
EP0147240B1 (en) | 1989-04-05 |
CA1284583C (en) | 1991-06-04 |
EP0147240A3 (en) | 1986-04-02 |
EP0247706A3 (en) | 1988-01-13 |
EP0247706B1 (en) | 1989-06-14 |
EP0251419A1 (en) | 1988-01-07 |
EP0251419B1 (en) | 1989-05-31 |
CA1284883C (en) | 1991-06-18 |
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