CA1270642A - Fuel compositions - Google Patents
Fuel compositionsInfo
- Publication number
- CA1270642A CA1270642A CA000470058A CA470058A CA1270642A CA 1270642 A CA1270642 A CA 1270642A CA 000470058 A CA000470058 A CA 000470058A CA 470058 A CA470058 A CA 470058A CA 1270642 A CA1270642 A CA 1270642A
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- Prior art keywords
- fuel
- hydrocarbyl
- coking
- amine
- combination
- Prior art date
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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
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
Abstract
ABSTRACT
FUEL COMPOSITIONS
Coking in and around the injector nozzles of indirect injection compression ignition engines is reduced by means of distillate fuel with which has been blended suitable concentrations of:
(a) organic nitrate ignition accelerator, and (b) hydrocarbyl-substituted succinimide, or (a) organic nitrate ignition accelarator, (c) hydrocarbyl amine having from 3 to 60 carbons and from 1 to 10 nitrogens, and (d) N,N'-disalicylidene-1,2-diaminopropane, or (b) hydrocarbyl-substituted succinimide or succinamide, (c) hydrocarbyl amine having from 3 to 60 carbons and from 1 to 10 nitrogens, and (d) N,N'-disalicylidene-1,2-diaminopropane.
Also described are such additive mixtures for use in distillate fuels in amounts sufficient to reduce the coking tendencies of such fuels when used in the opera-tion of indirect injection compression ignition engines.
FUEL COMPOSITIONS
Coking in and around the injector nozzles of indirect injection compression ignition engines is reduced by means of distillate fuel with which has been blended suitable concentrations of:
(a) organic nitrate ignition accelerator, and (b) hydrocarbyl-substituted succinimide, or (a) organic nitrate ignition accelarator, (c) hydrocarbyl amine having from 3 to 60 carbons and from 1 to 10 nitrogens, and (d) N,N'-disalicylidene-1,2-diaminopropane, or (b) hydrocarbyl-substituted succinimide or succinamide, (c) hydrocarbyl amine having from 3 to 60 carbons and from 1 to 10 nitrogens, and (d) N,N'-disalicylidene-1,2-diaminopropane.
Also described are such additive mixtures for use in distillate fuels in amounts sufficient to reduce the coking tendencies of such fuels when used in the opera-tion of indirect injection compression ignition engines.
Description
lZ7064~
Case 5250-Plus FUEL COMPOSITIONS
Compression ignition fuel compositions and additive mixtures of organic nitrate ignition accelerator and hydrocarbyl-substituted succinimide, in 5 amounts sufficient to resist the coking tendencies of compression ignition fuel compositions when used in the oDeration of indirect injection diesel engines.
Throttling diesel nozzles have recently come into widespread use in indirect injection automotive and 10 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 com-15 pleted. 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 n pi ntle nozzle").
Unfortunately, the advent of such engines has given rise to a new problem, that of excessive coking on 127~i642 the critical surfaces of the injectors that inject fuelinto the prechamber or swirl chamber of the engine. In particular and with reference to the Figure, the carbon tends to fill in all of the available corners and 5 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. In severe cases, carhon builds up on the form 12 and the obturator 10 to such an extent 10 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 15 combustion chamber pressure rise, and increased engine noise, and can also result in an excessive increase in emission from the engine of unburned hydrocarbons.
~ hile low fuel cetane nu~ber is believed to be a major contributing factor to the coking problem, it is 20 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.
In accordance with one of its embodiments, this invention provides distillate fuel for indirect injection compression ignition engines containing at least the combination of (a) organic nitrate ignition accelerator, and (b) hydrocarbyl-substituted succinimide or succinamide, or the combination of (a) organic nitrate ignition accelerator, (c) hydrocarbyl amine having from 3 to 60 carbons and from 1 to 10 nitrogens and (d) N,N'-disalicylidene-1,2-diaminopropane, or the combination of (b) hydrocarbyl-substituted succinimide or succinamide, (c) hydrocarbyl amine having from 3 to 60 carbons and from 1 to 10 nitrogens and (d) N,N'-disalicylidene-1,2-diaminopropane, said combinations being separately present in an amount sufficient to minimize coking, especially throttling nozzle coking, in the prechambers or swirl chambers of indirect injection compression ignition engines operated on such fuel.
Another embodiment of the present invention is a distillate fuel additive fluid composition comprising (a) organic nitrate ignition accelerator, and (b) hydrocarbyl-substituted succinimide or succinamide, or (a) organic nitrate ignition accelerator, (c) hydrocarbyl amine having from 3 to 60 carbons and from 1 to 10 nitrogens and (d) N,N'-~:~ rn/
3 2~Q64~2 disalicylidene~l,2-diaminopropane or (b) hydrocarbyl-substituted succinimide or succinamide, (c) hydrocarbyl amine having from 3 to 60 carbons and from 1 to 10 nitrogens and (d~ N,N'-disalicylidene-1,2-diaminopropane in an amount -sufficient to minimize the coking characteristics of such fuel, especially throttling nozzle coking, in the prechambers or swirl chambers of indirect compression ignition engines operated on such fuel.
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 co~ing, 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 at least the combination of (a) organic nitrate ignition accelerator, and (b) hydrocarbyl-substituted succinimide or succinamide, or the combination of (a) organic nitrate ignition accelerator, (c) hydrocarbyl amine having from 3 to 60 carbons and from 1 to 10 nitrogens and (d) N,N'-disalicylidene-1,2-diaminopropane or the combination of (b) hydrocarbyl-substituted succinimide or succinamide, (c) hydrocarbyl amine having from 3 to 60 carbons and from 1 to 10 nitrogens and (d) rn/
127(~64~2 N,N'-disalicyclidene-1,2-diaminopropane, said combina-tions being separately present in an amount sufficient to mini~ize 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 tendellcies of fuels used to operate indirect injection compression ignition engines. Such behavior was exhibited in a series of standard engine dynamometer tests conducted as des-cribed in Examples I, II and III hereinafter.
A wide variety of organic nitrate ignition accelerators, component (a), may be employed in the fuels of this invention. Preferred nitrate esters are 15 the aliphatic or cycloaliphatic nitrates in which the aliphatic or cycloaliphatic group is saturated, con-tains up to about 12 carbons and, optionally, may be substituted with one or more oxygen atoms.
Typical organic nitrates that may be used are 20 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 25 nitrate, isooctyl nitrate, 2-ethylhexyl nitrate, nonyl nitrate, decyl nitrate, undecyl nitrate, dodecyl ~Z7C~6~Z
nitrate, cyclopentyl nitrate, cyciohexyl nitrate, methyl-cyclohexyl nitrate, cycloclodecyl nitrate, 2-ethoxyethyl 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 oE this invention is a mixture of octyl nitrates available as an article of commerce from ~thyl Corporation under the trade mark DII-3 ignition improver.
The hydrocarbyl-substituted succinimides, component (~) 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 for~ a hydrocarbyl-substituted succinic anhydride. Reaction temperatures of 100-250C are used. ~ith higher boiling olefinically-unsaturated hydrocarbons, good results are obtained at 200-250C. 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, pro-p-ylene, isobutylene, l-hexene, l-decene and the like.
~seful copolymers are ethylene-propylene copolymers, ethylene-isobutylene copolymers, propylene-isobutylene copolymers, ethylene-l-decene copolymers and the like.
lZ7~:16~2 Hydrocarbyl substituents have also been made from olefin terpolymers. Very useful products have been made from ethylene-C3_l2 alpha olefin - C5_l2 non-conjugated diene terpolymers; such as ethylene-propylene-1,4-hexadiene terpolyrner; ethylene-propylene-l,5-cyclooctadiene terpolymer; ethylene-propylene-norbornene terpolymers and the like.
Of the foregoing, by far the most useful hydro-carbyl substituents are derived from butene polymers, especially polymers of isobutylene.
The molecular weight of the hydrocarbyl sub-stituent 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. ~xamples of these are methyl a-nine, dirnethyl amine, n-butyl amine, di-(n-dodecyl) amine, N-(arninoethyl) piperidine, piperazine, ~-(3-amino-pro~yl) piperazine, and the like.
~27Q~i~2 Preferably, the amine has at least one reactiveprimary anine group capable of reacting to form the preferred succinimides. Examples of such 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, dethylene 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 H2N-~ R - NH-~ H
~,7Q6~
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.
In a highly 2referred embodiment, the poly-alkylene amine is a polyethylenearnine containing 2-6 ethyleneamine units. These are represented by the above ~ormula in which R is the group -CH2CH2- 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.
Useful amine-alcohol products are described in U.S. 3,184,474; U.S. 3,576,743; U.S. 3,632,511; U.S.
3,804,763; U.S. 3,836,471; U.S. 3,936,480; rJ.s.
3,948,800; U.S. 3,950,341; U.S. 3,957,854; U.S.
3,957,855; U.S. 3,991,098; U.S. 4,071,548 and U.S.
4,173,540.
The reaction between the hydrocarbyl-substituted succinlc anhydride and the amine can be carried out by lZ7~642 ~ixing the com~onents 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 100-250C. 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 Ed~in Cooper Company under the trade mark HITEC ~-644. This product comprises a mixture of active ingredients and solvent. Thus, when HITEC~ E-644 is used as component (b) in formulating the fuels of this invention, 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 Einished blend contains an adequate quantity of the foregoing 20 succinimide-succinamide ingredient although smaller amounts may be successEully employed.
Tne 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 ~Z7~)6~
concentration of the ignition accelerator is 400 to 600 PTs (1.1436 to 1.7154 grams per liter).
It is not believed that there is anything critical as regards the maximum amount of components (a) and ~b) used in the fuel. Thus, the maximum amount of these components will probably be governed in any given situation by matters of choice and economics.
The coking-inhibiting components (a) and (b) oE
the invention can be added to the Euels 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 distil:Late fuels. In other words, part oE the present invention are coking inhibiting fluids which comprise organic nitrate ignition accelerator and hydrocarbyl-substituted succinimide-succinamide.
Use oE such fluids in addition to resulting in great convenience in storage, handling, transportation, blending with fuels, and so forth, also are potent concentrates ~hich serve the function oE inhibiting or mininizing the coking characteristics oE compression ~Z7~6g~
ignition distillate fuels used to operate indirect compression ignition engines.
In these fluid compositions, the amount of com-ponents (a) and (b) can vary widely. In general, the fluid compositions contain S to 95~ by weight of the organic nitrate ignition accelerator component and 5 to 95% by weight of the hydrocarbyl-substituted succinimide-succinamide component. Typically, from .01 by weight llp to 1.0% by weight of the combination will be sufficient to provide good coking-inhibiting proper-ties to the distillate fuel. 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.
Accordingly, a more preferred distillate fuel composition includes a hydrocarbyl amine in combination with the present additives.
~7~642 r~hile a variety of hydrocarbyl amines may be used in the fuel connositions of this invention, a primary aliphatic amine, the aliphatic group of which is tertiary, e.g., an amine of the fonnula:
wherein R is one or a mixture of tertiary aliphatic groups containing 8 to 18 or more (preferably 12-16) carhon atoms is preferred. Most preferably, these tertiary aliphatic groups are tertiary alkyl groups. It 10 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. ~o. 3,909,215 gives a description of the various hydrocarbyl amines having from 3 to 60 carbons and ~rom 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,.I-dimethylamine, ~nd N-alkyl,N,N-dimethylamines in which 20 the alkyl group is one or a combination of al~yl groups pre~erably having 8 to 18 or more carbon atoms.
A particularly preferred hydrocarbyl amine is available commercially ~rom the Rohm and Haas Company under the trade mark Primene 81R. The Primene 81R*is * trade mark ~75;~6~2 believed to be a mixture of primary aliphatic amines in which the aliphatic groups are predominantly Cl2 and Cl4 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.
Accordingly, another embodiment of the present invention is distillate fuel for indirect injection compression ignition engines containing at least the 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.
Also included as a further embodiment of the invention is a distillate fuel additive composition com2rising (a) organic nitrate ignition accelerator, (b) hydrocarbyl-substituted succinimide and (c) hydrocarbyl amine in an amount sufficient to minimize the coking characteristics of such fuel, especially throttling nozzle coking in the prechambers or swirl chambers in indirect injection compression ignition engines operated on such fuel.
~Z7~64;~
In general, these additive fuel compositions ~ill 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.
In a still further embodiment of the invention there is provided a method of inhibiting coking, especially throttling nozzle coking in the prechambers or s-~irl chambers of an indirect injection compression ignition engine which comprises supplying said engine ~ith a distillate fuel containing at least the com-bination of (a) organic nitrate ignition accelerator, (b) hydrocarbyl~substituted succinimide and (c) hydrocarbyl amine, said combination being present in an amount sufficient to minlmize such coking in an engine operated on such fuel.
Another additive which can be used to advantage in the present invention i5 a metal deactivator.
Examples oE these are salicylidene-o-aminophenol, 20 disalicylidene ethylenediamine and disalicylidene propylenediamine. ~ particularly preferred metal deactivator is N,N'-disalicylidene-1,2-diaminopropane (80 weight percent active in 20 weight percent toluene solvent) which is available as an article of commerce from Ethyl Corporation under the trade mark . ~ '~thyl" MDA.
~27~642 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), the me~al deactivator, preferably N,N'-disalicylidene-1,2-diaminopropane.
Accordingly, another embodiment of the present invention is distillate fuel for indirect injection compression ignition engines containing at least the combination of (a) organic nitrate ignition accelerator, (b) hydrocarbyl-substituted succinimide, (c) hydrocarbyl 10 amine, and (d) N,N'-disalicylidene-1,2-diaminopropane, said combination being present in an amount sufficient to minimize coking, expecially throttling nozzle coking in the prechambers or swirl chambers in indirect injection compression ignition engines operated on such 15 fuel.
Also included as a further embodiment of the invention is a distillate fuel additive composition comprising (a) organic nitrate ignition accelerator, (b) hydrocarbyl-substituted succinimide, (c) hydrocarbyl 20 amine, and (d) N,N'-disalicylidene-1,2-diaminopropane in an amount sufficient to minimize the coking charac-teristics of such fuel, especially throttling nozzle coking in the ?rechambers or swirl chambers of indirect injection compression ignition engines operated on such 25 fuels.
In general, these additive fuel compositions will contain as much as 50% by weight of the combination of lZ7Q6~
organic nitrate ignition accelerator and hydrocarbyl-substituted succinimide-succinamide and U2 to 50~ of the combination of hydrocarbyl amine and N,N'-disalicylidene-1,2-diaminopropane or other additives when they are present.
In a still further embodiment of the invention there is provided a method of inhibiting coking, especially throttling nozzle coking in the prechambers or swirl chambers in an indirect in]ection compression ignition engine which comprises supplying said engine with a distillate fuel containing at least the com-bination of (a) organic nitrate ignition accelerator, (b) hydrocarbyl-substituted succinimide, (c) hydrocarbyl amine and (d) ~,~'-disalicylidene-1,2-diaminopropane, 15 said combination being present in an amount to minimize such coking in an engine operated on such fuel.
In another embodiment of this invention, the coking-inhibiting components (a), (c) and (d) of the invention can be added to the fuels by any means known in the art for incorporating small quantities oE
additives into distillate fuels. Components (a), (c) and (d) can be added separately or they can be combined and added together. It is convenient to utilize additive fluid mixtures which consist oE organic nitrate ignition accelerator, hydrocarbyl amine and metal deactivator agents. These additive fluid mixtures are 127 L?~4Z
added to distillate fuels. In other words, part of the ~resent invention are coking inhibiting fluids which comprise organic nitrate ignition accelerator, hydrocarbyl amine having Erom 3 to 60 carbons and from 1 to 10 nitrogens and metal deactivator, preEerably disalicylidene-1,2-diaminopropane.
In these fluid compositions, the amount of components (a), (c) and (d) can vary widely. In general, the fluid compositions contain 10 to 97.9% by 10 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 O.Ql~ by weight up to 1.0% by weight of the combination of the components (a), (c) and a(d) will be 15 sufficient to pro~ide good coking-inhibiting properties to the distillate fuel. A preferred distillate Euel composition contains from 0.1 to 0.5~ by weight oE the combination containing rom 50 to 97.9% by weight of the organic nitrate ignition accelerator, from 2.0 to 45~ by 20 weight of the hydrocarbyl amine and Erom 0.1 to 5.0% by weight of the metal deactivator component.
In another embodiment of this invention, the coking-inhibiting components (b), (c) and (d) of the invention can be added to the fuels by any means known 25 in the art for incorporating small quantities of additives into distillate fuels. Components (b), (c) 127~6~2 and (d) can be added separately or they can be combined and added together. It is convenient to utilize additive fluid mixtures which consist of hydrocarbyl-substituted succinimide-succinamide agents, hydrocarbyl 5 amine and N,N ' -disalicylidene-1,2-diaminopropane These additive ~luid mixtures are added to distillate fuels.
In other words, part of the present invention are coking inhibiting fluids which comprise hydrocarbyl-substituted succinimide-succinamide, hydrocarbyl amine having from 3 10 to 60 carbons and 1 to 10 nitrogens, and metal deacti-vator, preferably N,N'-disalicylidene-1,2-diaminopropane In these fluid compositions, the amount of components (b), (c) and (d) can vary widely. In general, the fluid compositions contain 10 to 97.9% by 15 weight of the hydrocarbyl-substituted succinimide-succinamide component, 20 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 will be sufficient to 20 provide good coking-inhibiting properties to the dis-tillate 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 hydro-carbyl succinimide-succinamide component and from 2. OQ
25 to 45~ by weight of the hydrocarbyl amine and from n.
to 5.0% by weight of the metal deactivator, preferably N,~'-disalicylidene-1,2-diaminopropane.
1;27~6~2 The practice and advantages of this invention will become still further apparent from the following illustrative example.
EXA~PL~ 1 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 com-mercial diesel engine operated on a coking test cycle developed by Institute Francais Petrole and as prac-ticed by Peugeot S. A. The amount of coking together with a ~uantitative indication of the adverse consc-~uences of such coking was determined by means of ~i) injector air flow performance, (ii) emission of unburned hydrocarbons, (iii) englne 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.
The base fuel employed in these engine tests was a commercially-available diesel fuel having a nominal cetane rating of 42. PIA analysis indicated the fuel ~Z7~64Z
was composed by volume of 31.5~ aromatics, 3.0% olefins and 65.5~ saturates. Its distillation range (ASTM
~-158) was as follows:
~arometer 29.46 inches of Hg (0.9987 ~ars) Initial 406F - 207.78C
_ vaporated at F - at C
439 226.11 450 232.22 456 235.56 463 239,44 480 248.89 499 259.44 521 271.67 545 285.0 70 572 300.0 603 317.22 85 621 327.22 90 643 339.44 95 678 358.89 Final 678F 358.89 Recovery 97.5%
Residue 2.5 Loss None 127(~64~
Other inspection data on the base ~uel were asfollo~s:
~iner,latic Viscosity, (ASTM D-445) . . . 3.50 Centi-stokes, 40C
Pour Point (ASTM D-97). . . . . . . . .-26C
Cloud Point (ASTM D-97) . . . . . . . . 33C
- Flash Point (ASTM D-93) . . . . . . . 91C
Steam Jet Gum . . . . . . . . . . . . . 2.4 mg~l00 ml Aniline Point (ASTM D-611). . . . . . . 143.4F (61.89C) 10 Total Sulfur. . ~ . . . . . . . . . . . 0.41 wt. %
Ramsbottom Carbon, ~ (ASTM D-524) . . . 0.1460 on 10 Residuum Gravity (ASTM D-287). . . . . . . . . . 31.8 API
Specific Gravity @ 25C . . . . . . . . 0.86 Cetane rating . . . . . . . . . . . . . 41 A test blend was prepared from this base fuel (Fuel A). Fuel A contained a combination of (i) 506 PTB
(1.447 grams/liter) of mixed octyl nitrates (a com-mercial product available ~rom Ethyl Corporation under 20 the trade mark DII-3 Ignition Improver), (ii) 41 PT3 (0.117 gram/liter) of HITEC E-644, a product o~ Edwin Cooper, Inc., believed to be a hydrocarbyl succinimide-succinamide made by reacting two moles of a polyisobutenyl succinic anhydride (PIBSA) ~ith one mole of a polyethylene amine mixture having an average composition corresponding to tetraethylene pentamine, ~Z70642 (iii) 14 PT3 (0.04 grams/liter) of a hydrocarbyl amine available commercially from Rohm and Haas Company under the trade mark Primene 81~ and (iv) 1.7 plrB (o.on4s6 grams/liter) of Ethyl* Metal Deactivator, a product of Ethyl Corporation, the active ingredient of which is N,~'-disalicylidene-1,2-diaminopropane. The manu-facturer gives the following typical properties foe its HITEC~ E-5 44 product:
Appearance Dark brown viscou.s liquid Nitrogen, wt. % 2.0 Specific Gravity at 60/60F o. 928 Viscosity at 210F, cs 340 (9s.89oc) The Primene 81~*is believed to be a mixture of primary aliphatic amines in which the aliphatic grouos are predominantly C12 and C14 tertiary alkyl groups.
The manufacturer gives the following typical properties for its Ethyl* metal Deactivator:
Form Liquid Color Amber Density, at 68F
g/ml 1.0672 lb/gal 8.91 Active ingredient, wt % 80 * trade mark 127~64t2 Solvent vehicle (toluene), wt % 20 Flash point, open cup, F 84 (28.89C) Fire point, F 100 (37.78C) Solubility In gasoline (Typical) Saturated solution contains 94~ M~.
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. Aeter this warm-up, the engine was subjected to the following automatic cycle:
Event RPM Beam Load Minutes EGR
1 750 0 4 off
Case 5250-Plus FUEL COMPOSITIONS
Compression ignition fuel compositions and additive mixtures of organic nitrate ignition accelerator and hydrocarbyl-substituted succinimide, in 5 amounts sufficient to resist the coking tendencies of compression ignition fuel compositions when used in the oDeration of indirect injection diesel engines.
Throttling diesel nozzles have recently come into widespread use in indirect injection automotive and 10 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 com-15 pleted. 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 n pi ntle nozzle").
Unfortunately, the advent of such engines has given rise to a new problem, that of excessive coking on 127~i642 the critical surfaces of the injectors that inject fuelinto the prechamber or swirl chamber of the engine. In particular and with reference to the Figure, the carbon tends to fill in all of the available corners and 5 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. In severe cases, carhon builds up on the form 12 and the obturator 10 to such an extent 10 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 15 combustion chamber pressure rise, and increased engine noise, and can also result in an excessive increase in emission from the engine of unburned hydrocarbons.
~ hile low fuel cetane nu~ber is believed to be a major contributing factor to the coking problem, it is 20 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.
In accordance with one of its embodiments, this invention provides distillate fuel for indirect injection compression ignition engines containing at least the combination of (a) organic nitrate ignition accelerator, and (b) hydrocarbyl-substituted succinimide or succinamide, or the combination of (a) organic nitrate ignition accelerator, (c) hydrocarbyl amine having from 3 to 60 carbons and from 1 to 10 nitrogens and (d) N,N'-disalicylidene-1,2-diaminopropane, or the combination of (b) hydrocarbyl-substituted succinimide or succinamide, (c) hydrocarbyl amine having from 3 to 60 carbons and from 1 to 10 nitrogens and (d) N,N'-disalicylidene-1,2-diaminopropane, said combinations being separately present in an amount sufficient to minimize coking, especially throttling nozzle coking, in the prechambers or swirl chambers of indirect injection compression ignition engines operated on such fuel.
Another embodiment of the present invention is a distillate fuel additive fluid composition comprising (a) organic nitrate ignition accelerator, and (b) hydrocarbyl-substituted succinimide or succinamide, or (a) organic nitrate ignition accelerator, (c) hydrocarbyl amine having from 3 to 60 carbons and from 1 to 10 nitrogens and (d) N,N'-~:~ rn/
3 2~Q64~2 disalicylidene~l,2-diaminopropane or (b) hydrocarbyl-substituted succinimide or succinamide, (c) hydrocarbyl amine having from 3 to 60 carbons and from 1 to 10 nitrogens and (d~ N,N'-disalicylidene-1,2-diaminopropane in an amount -sufficient to minimize the coking characteristics of such fuel, especially throttling nozzle coking, in the prechambers or swirl chambers of indirect compression ignition engines operated on such fuel.
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 co~ing, 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 at least the combination of (a) organic nitrate ignition accelerator, and (b) hydrocarbyl-substituted succinimide or succinamide, or the combination of (a) organic nitrate ignition accelerator, (c) hydrocarbyl amine having from 3 to 60 carbons and from 1 to 10 nitrogens and (d) N,N'-disalicylidene-1,2-diaminopropane or the combination of (b) hydrocarbyl-substituted succinimide or succinamide, (c) hydrocarbyl amine having from 3 to 60 carbons and from 1 to 10 nitrogens and (d) rn/
127(~64~2 N,N'-disalicyclidene-1,2-diaminopropane, said combina-tions being separately present in an amount sufficient to mini~ize 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 tendellcies of fuels used to operate indirect injection compression ignition engines. Such behavior was exhibited in a series of standard engine dynamometer tests conducted as des-cribed in Examples I, II and III hereinafter.
A wide variety of organic nitrate ignition accelerators, component (a), may be employed in the fuels of this invention. Preferred nitrate esters are 15 the aliphatic or cycloaliphatic nitrates in which the aliphatic or cycloaliphatic group is saturated, con-tains up to about 12 carbons and, optionally, may be substituted with one or more oxygen atoms.
Typical organic nitrates that may be used are 20 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 25 nitrate, isooctyl nitrate, 2-ethylhexyl nitrate, nonyl nitrate, decyl nitrate, undecyl nitrate, dodecyl ~Z7C~6~Z
nitrate, cyclopentyl nitrate, cyciohexyl nitrate, methyl-cyclohexyl nitrate, cycloclodecyl nitrate, 2-ethoxyethyl 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 oE this invention is a mixture of octyl nitrates available as an article of commerce from ~thyl Corporation under the trade mark DII-3 ignition improver.
The hydrocarbyl-substituted succinimides, component (~) 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 for~ a hydrocarbyl-substituted succinic anhydride. Reaction temperatures of 100-250C are used. ~ith higher boiling olefinically-unsaturated hydrocarbons, good results are obtained at 200-250C. 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, pro-p-ylene, isobutylene, l-hexene, l-decene and the like.
~seful copolymers are ethylene-propylene copolymers, ethylene-isobutylene copolymers, propylene-isobutylene copolymers, ethylene-l-decene copolymers and the like.
lZ7~:16~2 Hydrocarbyl substituents have also been made from olefin terpolymers. Very useful products have been made from ethylene-C3_l2 alpha olefin - C5_l2 non-conjugated diene terpolymers; such as ethylene-propylene-1,4-hexadiene terpolyrner; ethylene-propylene-l,5-cyclooctadiene terpolymer; ethylene-propylene-norbornene terpolymers and the like.
Of the foregoing, by far the most useful hydro-carbyl substituents are derived from butene polymers, especially polymers of isobutylene.
The molecular weight of the hydrocarbyl sub-stituent 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. ~xamples of these are methyl a-nine, dirnethyl amine, n-butyl amine, di-(n-dodecyl) amine, N-(arninoethyl) piperidine, piperazine, ~-(3-amino-pro~yl) piperazine, and the like.
~27Q~i~2 Preferably, the amine has at least one reactiveprimary anine group capable of reacting to form the preferred succinimides. Examples of such 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, dethylene 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 H2N-~ R - NH-~ H
~,7Q6~
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.
In a highly 2referred embodiment, the poly-alkylene amine is a polyethylenearnine containing 2-6 ethyleneamine units. These are represented by the above ~ormula in which R is the group -CH2CH2- 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.
Useful amine-alcohol products are described in U.S. 3,184,474; U.S. 3,576,743; U.S. 3,632,511; U.S.
3,804,763; U.S. 3,836,471; U.S. 3,936,480; rJ.s.
3,948,800; U.S. 3,950,341; U.S. 3,957,854; U.S.
3,957,855; U.S. 3,991,098; U.S. 4,071,548 and U.S.
4,173,540.
The reaction between the hydrocarbyl-substituted succinlc anhydride and the amine can be carried out by lZ7~642 ~ixing the com~onents 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 100-250C. 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 Ed~in Cooper Company under the trade mark HITEC ~-644. This product comprises a mixture of active ingredients and solvent. Thus, when HITEC~ E-644 is used as component (b) in formulating the fuels of this invention, 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 Einished blend contains an adequate quantity of the foregoing 20 succinimide-succinamide ingredient although smaller amounts may be successEully employed.
Tne 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 ~Z7~)6~
concentration of the ignition accelerator is 400 to 600 PTs (1.1436 to 1.7154 grams per liter).
It is not believed that there is anything critical as regards the maximum amount of components (a) and ~b) used in the fuel. Thus, the maximum amount of these components will probably be governed in any given situation by matters of choice and economics.
The coking-inhibiting components (a) and (b) oE
the invention can be added to the Euels 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 distil:Late fuels. In other words, part oE the present invention are coking inhibiting fluids which comprise organic nitrate ignition accelerator and hydrocarbyl-substituted succinimide-succinamide.
Use oE such fluids in addition to resulting in great convenience in storage, handling, transportation, blending with fuels, and so forth, also are potent concentrates ~hich serve the function oE inhibiting or mininizing the coking characteristics oE compression ~Z7~6g~
ignition distillate fuels used to operate indirect compression ignition engines.
In these fluid compositions, the amount of com-ponents (a) and (b) can vary widely. In general, the fluid compositions contain S to 95~ by weight of the organic nitrate ignition accelerator component and 5 to 95% by weight of the hydrocarbyl-substituted succinimide-succinamide component. Typically, from .01 by weight llp to 1.0% by weight of the combination will be sufficient to provide good coking-inhibiting proper-ties to the distillate fuel. 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.
Accordingly, a more preferred distillate fuel composition includes a hydrocarbyl amine in combination with the present additives.
~7~642 r~hile a variety of hydrocarbyl amines may be used in the fuel connositions of this invention, a primary aliphatic amine, the aliphatic group of which is tertiary, e.g., an amine of the fonnula:
wherein R is one or a mixture of tertiary aliphatic groups containing 8 to 18 or more (preferably 12-16) carhon atoms is preferred. Most preferably, these tertiary aliphatic groups are tertiary alkyl groups. It 10 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. ~o. 3,909,215 gives a description of the various hydrocarbyl amines having from 3 to 60 carbons and ~rom 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,.I-dimethylamine, ~nd N-alkyl,N,N-dimethylamines in which 20 the alkyl group is one or a combination of al~yl groups pre~erably having 8 to 18 or more carbon atoms.
A particularly preferred hydrocarbyl amine is available commercially ~rom the Rohm and Haas Company under the trade mark Primene 81R. The Primene 81R*is * trade mark ~75;~6~2 believed to be a mixture of primary aliphatic amines in which the aliphatic groups are predominantly Cl2 and Cl4 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.
Accordingly, another embodiment of the present invention is distillate fuel for indirect injection compression ignition engines containing at least the 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.
Also included as a further embodiment of the invention is a distillate fuel additive composition com2rising (a) organic nitrate ignition accelerator, (b) hydrocarbyl-substituted succinimide and (c) hydrocarbyl amine in an amount sufficient to minimize the coking characteristics of such fuel, especially throttling nozzle coking in the prechambers or swirl chambers in indirect injection compression ignition engines operated on such fuel.
~Z7~64;~
In general, these additive fuel compositions ~ill 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.
In a still further embodiment of the invention there is provided a method of inhibiting coking, especially throttling nozzle coking in the prechambers or s-~irl chambers of an indirect injection compression ignition engine which comprises supplying said engine ~ith a distillate fuel containing at least the com-bination of (a) organic nitrate ignition accelerator, (b) hydrocarbyl~substituted succinimide and (c) hydrocarbyl amine, said combination being present in an amount sufficient to minlmize such coking in an engine operated on such fuel.
Another additive which can be used to advantage in the present invention i5 a metal deactivator.
Examples oE these are salicylidene-o-aminophenol, 20 disalicylidene ethylenediamine and disalicylidene propylenediamine. ~ particularly preferred metal deactivator is N,N'-disalicylidene-1,2-diaminopropane (80 weight percent active in 20 weight percent toluene solvent) which is available as an article of commerce from Ethyl Corporation under the trade mark . ~ '~thyl" MDA.
~27~642 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), the me~al deactivator, preferably N,N'-disalicylidene-1,2-diaminopropane.
Accordingly, another embodiment of the present invention is distillate fuel for indirect injection compression ignition engines containing at least the combination of (a) organic nitrate ignition accelerator, (b) hydrocarbyl-substituted succinimide, (c) hydrocarbyl 10 amine, and (d) N,N'-disalicylidene-1,2-diaminopropane, said combination being present in an amount sufficient to minimize coking, expecially throttling nozzle coking in the prechambers or swirl chambers in indirect injection compression ignition engines operated on such 15 fuel.
Also included as a further embodiment of the invention is a distillate fuel additive composition comprising (a) organic nitrate ignition accelerator, (b) hydrocarbyl-substituted succinimide, (c) hydrocarbyl 20 amine, and (d) N,N'-disalicylidene-1,2-diaminopropane in an amount sufficient to minimize the coking charac-teristics of such fuel, especially throttling nozzle coking in the ?rechambers or swirl chambers of indirect injection compression ignition engines operated on such 25 fuels.
In general, these additive fuel compositions will contain as much as 50% by weight of the combination of lZ7Q6~
organic nitrate ignition accelerator and hydrocarbyl-substituted succinimide-succinamide and U2 to 50~ of the combination of hydrocarbyl amine and N,N'-disalicylidene-1,2-diaminopropane or other additives when they are present.
In a still further embodiment of the invention there is provided a method of inhibiting coking, especially throttling nozzle coking in the prechambers or swirl chambers in an indirect in]ection compression ignition engine which comprises supplying said engine with a distillate fuel containing at least the com-bination of (a) organic nitrate ignition accelerator, (b) hydrocarbyl-substituted succinimide, (c) hydrocarbyl amine and (d) ~,~'-disalicylidene-1,2-diaminopropane, 15 said combination being present in an amount to minimize such coking in an engine operated on such fuel.
In another embodiment of this invention, the coking-inhibiting components (a), (c) and (d) of the invention can be added to the fuels by any means known in the art for incorporating small quantities oE
additives into distillate fuels. Components (a), (c) and (d) can be added separately or they can be combined and added together. It is convenient to utilize additive fluid mixtures which consist oE organic nitrate ignition accelerator, hydrocarbyl amine and metal deactivator agents. These additive fluid mixtures are 127 L?~4Z
added to distillate fuels. In other words, part of the ~resent invention are coking inhibiting fluids which comprise organic nitrate ignition accelerator, hydrocarbyl amine having Erom 3 to 60 carbons and from 1 to 10 nitrogens and metal deactivator, preEerably disalicylidene-1,2-diaminopropane.
In these fluid compositions, the amount of components (a), (c) and (d) can vary widely. In general, the fluid compositions contain 10 to 97.9% by 10 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 O.Ql~ by weight up to 1.0% by weight of the combination of the components (a), (c) and a(d) will be 15 sufficient to pro~ide good coking-inhibiting properties to the distillate fuel. A preferred distillate Euel composition contains from 0.1 to 0.5~ by weight oE the combination containing rom 50 to 97.9% by weight of the organic nitrate ignition accelerator, from 2.0 to 45~ by 20 weight of the hydrocarbyl amine and Erom 0.1 to 5.0% by weight of the metal deactivator component.
In another embodiment of this invention, the coking-inhibiting components (b), (c) and (d) of the invention can be added to the fuels by any means known 25 in the art for incorporating small quantities of additives into distillate fuels. Components (b), (c) 127~6~2 and (d) can be added separately or they can be combined and added together. It is convenient to utilize additive fluid mixtures which consist of hydrocarbyl-substituted succinimide-succinamide agents, hydrocarbyl 5 amine and N,N ' -disalicylidene-1,2-diaminopropane These additive ~luid mixtures are added to distillate fuels.
In other words, part of the present invention are coking inhibiting fluids which comprise hydrocarbyl-substituted succinimide-succinamide, hydrocarbyl amine having from 3 10 to 60 carbons and 1 to 10 nitrogens, and metal deacti-vator, preferably N,N'-disalicylidene-1,2-diaminopropane In these fluid compositions, the amount of components (b), (c) and (d) can vary widely. In general, the fluid compositions contain 10 to 97.9% by 15 weight of the hydrocarbyl-substituted succinimide-succinamide component, 20 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 will be sufficient to 20 provide good coking-inhibiting properties to the dis-tillate 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 hydro-carbyl succinimide-succinamide component and from 2. OQ
25 to 45~ by weight of the hydrocarbyl amine and from n.
to 5.0% by weight of the metal deactivator, preferably N,~'-disalicylidene-1,2-diaminopropane.
1;27~6~2 The practice and advantages of this invention will become still further apparent from the following illustrative example.
EXA~PL~ 1 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 com-mercial diesel engine operated on a coking test cycle developed by Institute Francais Petrole and as prac-ticed by Peugeot S. A. The amount of coking together with a ~uantitative indication of the adverse consc-~uences of such coking was determined by means of ~i) injector air flow performance, (ii) emission of unburned hydrocarbons, (iii) englne 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.
The base fuel employed in these engine tests was a commercially-available diesel fuel having a nominal cetane rating of 42. PIA analysis indicated the fuel ~Z7~64Z
was composed by volume of 31.5~ aromatics, 3.0% olefins and 65.5~ saturates. Its distillation range (ASTM
~-158) was as follows:
~arometer 29.46 inches of Hg (0.9987 ~ars) Initial 406F - 207.78C
_ vaporated at F - at C
439 226.11 450 232.22 456 235.56 463 239,44 480 248.89 499 259.44 521 271.67 545 285.0 70 572 300.0 603 317.22 85 621 327.22 90 643 339.44 95 678 358.89 Final 678F 358.89 Recovery 97.5%
Residue 2.5 Loss None 127(~64~
Other inspection data on the base ~uel were asfollo~s:
~iner,latic Viscosity, (ASTM D-445) . . . 3.50 Centi-stokes, 40C
Pour Point (ASTM D-97). . . . . . . . .-26C
Cloud Point (ASTM D-97) . . . . . . . . 33C
- Flash Point (ASTM D-93) . . . . . . . 91C
Steam Jet Gum . . . . . . . . . . . . . 2.4 mg~l00 ml Aniline Point (ASTM D-611). . . . . . . 143.4F (61.89C) 10 Total Sulfur. . ~ . . . . . . . . . . . 0.41 wt. %
Ramsbottom Carbon, ~ (ASTM D-524) . . . 0.1460 on 10 Residuum Gravity (ASTM D-287). . . . . . . . . . 31.8 API
Specific Gravity @ 25C . . . . . . . . 0.86 Cetane rating . . . . . . . . . . . . . 41 A test blend was prepared from this base fuel (Fuel A). Fuel A contained a combination of (i) 506 PTB
(1.447 grams/liter) of mixed octyl nitrates (a com-mercial product available ~rom Ethyl Corporation under 20 the trade mark DII-3 Ignition Improver), (ii) 41 PT3 (0.117 gram/liter) of HITEC E-644, a product o~ Edwin Cooper, Inc., believed to be a hydrocarbyl succinimide-succinamide made by reacting two moles of a polyisobutenyl succinic anhydride (PIBSA) ~ith one mole of a polyethylene amine mixture having an average composition corresponding to tetraethylene pentamine, ~Z70642 (iii) 14 PT3 (0.04 grams/liter) of a hydrocarbyl amine available commercially from Rohm and Haas Company under the trade mark Primene 81~ and (iv) 1.7 plrB (o.on4s6 grams/liter) of Ethyl* Metal Deactivator, a product of Ethyl Corporation, the active ingredient of which is N,~'-disalicylidene-1,2-diaminopropane. The manu-facturer gives the following typical properties foe its HITEC~ E-5 44 product:
Appearance Dark brown viscou.s liquid Nitrogen, wt. % 2.0 Specific Gravity at 60/60F o. 928 Viscosity at 210F, cs 340 (9s.89oc) The Primene 81~*is believed to be a mixture of primary aliphatic amines in which the aliphatic grouos are predominantly C12 and C14 tertiary alkyl groups.
The manufacturer gives the following typical properties for its Ethyl* metal Deactivator:
Form Liquid Color Amber Density, at 68F
g/ml 1.0672 lb/gal 8.91 Active ingredient, wt % 80 * trade mark 127~64t2 Solvent vehicle (toluene), wt % 20 Flash point, open cup, F 84 (28.89C) Fire point, F 100 (37.78C) Solubility In gasoline (Typical) Saturated solution contains 94~ M~.
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. Aeter this warm-up, the engine was subjected to the following automatic cycle:
Event RPM Beam Load Minutes EGR
1 750 0 4 off
2 2750 12.0 6 on
3 1500 6.2 6 on
4 4000 16.2 4 o~f * trade mark lZ7Q~
- 25 ~
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.
~hen passing from one event to the next event in the above cycle, some time, of course, was re~uired to enable the engine to accelerate or decelerate from one speed to the next. Thus, more specifically, the above cycle was programmed as follows:
10SegmentSeconds ~m Beam Load 3 3* 2500 12 4 7* 2750 12 6 3* 2275 6.2 7 7* 1500 6.2 8 330 lS00 6.2 9 3* 3500 16.2 2010 7* 4000 16.2 11 230 4000 16.2 12 3* 2000 0 13 7* 750 0 25 * Represents two mode periods for acceleration or deceleration to the next condition.
lZ~Q64Z
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 Erom 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.
10 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 C~C deposit rating system.
The most significant test results are given in Table I, in which air flow is expressed as cc/min an~
hydrocarbon emissions as ppm.
TABLE I
Air Flow Pintle Obturator Hydrocarbon @ 0.1 mm Deposits Noise, ~B Emissions Fuel LiEt (10 = clean) EOT* INC~. EOT* Incr.
Base 36 8.0 83.8 3.0 577 406 A 38 8.6 81.4 1.9 275 1~3 * Value at end of test; the increase (Incr.) shown is in comparison to the value at start of test.
1Z7(~64Z
The results presented in Table I show that there were less coking deposits (higher air flow rate and fewer deposits), less engine noise and less hydrocarbon emissions with Fuel A, the fuel of the invention, as compared to the Base Fuel.
E~AMPLE II
A test blend was prepared from the base fuel of Example I (Fuel B). Fuel 3 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 trade mark 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 trade mark 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 ~,~'-disalicylidene-1,2-diamino-propane The test engine was operated under the same con-ditions as those of Example I.
The most significant test results are given inTahle II, in which air flow is expressed as cc/min and hydrocarbon emissions as ppm.
.
* trade mark :127Q64Z
T~BIE II
J
Air Flow Pintle Obturator Hydrocarbon @ 0.1 mm Deposits Noise, ~B Emissions Fuel Lift (10 = clean) EOT* I~CR. EOT* Incr.
Base 36 8.0 83.8 3.0 577 406 3 49 8.4 81.3 2.2 282 51 * Value at end of test: the increase (Incr.) shown is in comparison to the value at start of test.
The results presented in Table II show that there were less coking deposits thigher air flow rate and fewer deposits), less engine noise and less hydrocarbon emissions with Fuel ~, the fuel of the invention, as compared to the Base Fuel.
EXAMPLE III
A test blend was prepared from the hase fuel of Example I (Fuel C). Fuel C contained a combination of (i) 41 PTB (0.117 grams per liter) of HITEC E-644, a product of Edwin Cooperr Inc., helieved to be a hydro-carbyl succinimide-succinamide made by reacting two moles of a polyisobutenyl succinic anhydride (PI3SA) with one mole of a polyethylene amine mixture having an average composition corresponding to tetraethylene pentamine, (ii) 14 PTB (0.04 grams per liter) of a hydrocarbyl amine available commercially from Rohm and Haas Company under the trade mark Primene 81~, and 1~7Q642 (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,~'-disalicylidene-1,2-diamino-propane.
The test engine was operated unde the same con-ditions as those of Example I. The most significant test results are given in Table III, in which air flow is expressed as cc/min and hydrocarbon emissions as ppm.
TABLE III
Air Flow Pintle Obturator ~ydrocarbon @ 0.1 mm Deposits Noise, DB Emissions Fuel Lift (10 = clean) EOT* INCR. EOT* Incr.
Base 36 8.0 83.8 3.0 577 406 C 40 8.5 83.2 3.0 513 278 * Value at end of test; the increase (Incr.) shown is in comparison to the value at start of test.
The results presented in Table III show that there were less coking deposits (higher air flow rate and fewer deposits), less engine noise and less hydrocarbon emissions with Fuel C, the fuel of the invention, as compared to the Base Fuel.
# trade mark
- 25 ~
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.
~hen passing from one event to the next event in the above cycle, some time, of course, was re~uired to enable the engine to accelerate or decelerate from one speed to the next. Thus, more specifically, the above cycle was programmed as follows:
10SegmentSeconds ~m Beam Load 3 3* 2500 12 4 7* 2750 12 6 3* 2275 6.2 7 7* 1500 6.2 8 330 lS00 6.2 9 3* 3500 16.2 2010 7* 4000 16.2 11 230 4000 16.2 12 3* 2000 0 13 7* 750 0 25 * Represents two mode periods for acceleration or deceleration to the next condition.
lZ~Q64Z
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 Erom 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.
10 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 C~C deposit rating system.
The most significant test results are given in Table I, in which air flow is expressed as cc/min an~
hydrocarbon emissions as ppm.
TABLE I
Air Flow Pintle Obturator Hydrocarbon @ 0.1 mm Deposits Noise, ~B Emissions Fuel LiEt (10 = clean) EOT* INC~. EOT* Incr.
Base 36 8.0 83.8 3.0 577 406 A 38 8.6 81.4 1.9 275 1~3 * Value at end of test; the increase (Incr.) shown is in comparison to the value at start of test.
1Z7(~64Z
The results presented in Table I show that there were less coking deposits (higher air flow rate and fewer deposits), less engine noise and less hydrocarbon emissions with Fuel A, the fuel of the invention, as compared to the Base Fuel.
E~AMPLE II
A test blend was prepared from the base fuel of Example I (Fuel B). Fuel 3 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 trade mark 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 trade mark 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 ~,~'-disalicylidene-1,2-diamino-propane The test engine was operated under the same con-ditions as those of Example I.
The most significant test results are given inTahle II, in which air flow is expressed as cc/min and hydrocarbon emissions as ppm.
.
* trade mark :127Q64Z
T~BIE II
J
Air Flow Pintle Obturator Hydrocarbon @ 0.1 mm Deposits Noise, ~B Emissions Fuel Lift (10 = clean) EOT* I~CR. EOT* Incr.
Base 36 8.0 83.8 3.0 577 406 3 49 8.4 81.3 2.2 282 51 * Value at end of test: the increase (Incr.) shown is in comparison to the value at start of test.
The results presented in Table II show that there were less coking deposits thigher air flow rate and fewer deposits), less engine noise and less hydrocarbon emissions with Fuel ~, the fuel of the invention, as compared to the Base Fuel.
EXAMPLE III
A test blend was prepared from the hase fuel of Example I (Fuel C). Fuel C contained a combination of (i) 41 PTB (0.117 grams per liter) of HITEC E-644, a product of Edwin Cooperr Inc., helieved to be a hydro-carbyl succinimide-succinamide made by reacting two moles of a polyisobutenyl succinic anhydride (PI3SA) with one mole of a polyethylene amine mixture having an average composition corresponding to tetraethylene pentamine, (ii) 14 PTB (0.04 grams per liter) of a hydrocarbyl amine available commercially from Rohm and Haas Company under the trade mark Primene 81~, and 1~7Q642 (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,~'-disalicylidene-1,2-diamino-propane.
The test engine was operated unde the same con-ditions as those of Example I. The most significant test results are given in Table III, in which air flow is expressed as cc/min and hydrocarbon emissions as ppm.
TABLE III
Air Flow Pintle Obturator ~ydrocarbon @ 0.1 mm Deposits Noise, DB Emissions Fuel Lift (10 = clean) EOT* INCR. EOT* Incr.
Base 36 8.0 83.8 3.0 577 406 C 40 8.5 83.2 3.0 513 278 * Value at end of test; the increase (Incr.) shown is in comparison to the value at start of test.
The results presented in Table III show that there were less coking deposits (higher air flow rate and fewer deposits), less engine noise and less hydrocarbon emissions with Fuel C, the fuel of the invention, as compared to the Base Fuel.
# trade mark
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Distillate fuel for indirect injection, compression ignition engines, containing the combination of (a) an organic nitrate ignition accelerator and (b) a hydrocarbyl-substituted succinimide or succinamide, said combination being present in an amount sufficient to minimize coking in the nozzles of indirect injection, compression ignition engines operated on such fuel.
2. The fuel of claim 1, wherein said ignition accelerator is a mixture of octyl nitrates.
3. The fuel of claim 1, wherein said hydrocarbyl-substituted succinimide is an olefin polymer substituted succinimide, wherein said olefin polymer substituent has an average molecular weight of 500-500,000.
4. The fuel of claim 3, wherein the succinimide portion is derived from a polyalkyleneamine having the general formula:
H2N?R-NH?nH, wherein R is a divalent aliphatic hydrocarbon group having 2-4 carbon atoms and n is an integer from 1-10, including mixtures of the polyalkyleneamines.
H2N?R-NH?nH, wherein R is a divalent aliphatic hydrocarbon group having 2-4 carbon atoms and n is an integer from 1-10, including mixtures of the polyalkyleneamines.
5. The fuel of claim 4, wherein said olefin polymer substituent is a polyisobutene substituent having an average molecular weight of 700-5,000.
6. The fuel of claim 5, wherein said polyalkyleneamine is a polyethyleneamine having 2-6 ethylene amine units.
7. The fuel of claim 1, wherein the combination further includes (c) a hydrocarbyl amine having from 3 to 60 carbons and from one to 10 nitrogens.
8. The fuel of claim 7, wherein the combination further includes (d) N,N'-disalicyclidene-1,2-diaminopropane.
9. An additive fluid concentrate for use in distillate fuels, containing the combination of claim 1.
10. The additive fluid concentrate of claim 9, wherein the combination further includes (c) a hydrocarbyl amine having from 3 to 60 carbons and from one to 10 nitrogens and (d) N,N'-disalicyclidene-1,2-diaminopropane.
11. A method of inhibiting coking on the injector nozzles of indirect injection, compression ignition engines, comprising:
supplying the engine with a distillate fuel containing the combination of claim 1, 7 or 8, and being present in an amount sufficient to minimize such coking in the engine operated on such fuel.
supplying the engine with a distillate fuel containing the combination of claim 1, 7 or 8, and being present in an amount sufficient to minimize such coking in the engine operated on such fuel.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/567,089 US4482356A (en) | 1983-12-30 | 1983-12-30 | Diesel fuel containing alkenyl succinimide |
| US567,089 | 1983-12-30 | ||
| US06/567,090 US4482357A (en) | 1983-12-30 | 1983-12-30 | Fuel Compositions |
| US06/567,071 US4482355A (en) | 1983-12-30 | 1983-12-30 | Diesel fuel compositions |
| US567,071 | 1983-12-30 | ||
| US567,090 | 1983-12-30 |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000615609A Division CA1284883C (en) | 1983-12-30 | 1990-01-19 | Fuel compositions |
| CA000615608A Division CA1284583C (en) | 1983-12-30 | 1990-01-19 | Fuel compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1270642A true CA1270642A (en) | 1990-06-26 |
Family
ID=27416008
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000470058A Expired - Fee Related CA1270642A (en) | 1983-12-30 | 1984-12-13 | Fuel compositions |
| CA000615608A Expired - Fee Related CA1284583C (en) | 1983-12-30 | 1990-01-19 | Fuel compositions |
| CA000615609A Expired - Fee Related CA1284883C (en) | 1983-12-30 | 1990-01-19 | Fuel compositions |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000615608A Expired - Fee Related CA1284583C (en) | 1983-12-30 | 1990-01-19 | Fuel compositions |
| CA000615609A Expired - Fee Related CA1284883C (en) | 1983-12-30 | 1990-01-19 | Fuel compositions |
Country Status (2)
| Country | Link |
|---|---|
| EP (3) | EP0147240B1 (en) |
| CA (3) | CA1270642A (en) |
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| BR112023021674A2 (en) | 2021-04-26 | 2023-12-19 | Shell Int Research | FUEL COMPOSITION, AND, METHODS FOR IMPROVING POWER OUTPUT, FOR IMPROVING ACCELERATION, FOR REDUCE THE BURNING DURATION OF A FUEL COMPOSITION, AND FOR INCREASING THE FLAME SPEED OF A FUEL COMPOSITION IN AN INTERNAL COMBUSTION ENGINE |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2768884A (en) * | 1952-11-12 | 1956-10-30 | Sun Oil Co | Corrosion prevention |
| US2945749A (en) * | 1956-04-18 | 1960-07-19 | Socony Mobil Oil Co Inc | Stabilized fuel oil containing tertiary alkyl primary amines |
| NL120517C (en) * | 1960-12-16 | |||
| US3490882A (en) * | 1966-08-11 | 1970-01-20 | Du Pont | Stabilized distillate fuel oils and additive compositions therefor |
| US3701641A (en) * | 1969-08-29 | 1972-10-31 | Cities Service Oil Co | Stabilized distillate hydrocarbon fuel oil compositions and additives therefor |
| US3717446A (en) * | 1970-12-31 | 1973-02-20 | Union Oil Co | Gasoline anti-icing additives (a) |
| US3709668A (en) * | 1971-06-30 | 1973-01-09 | Exxon Research Engineering Co | Gasoline composition providing enhanced engine operation |
| US4208190A (en) * | 1979-02-09 | 1980-06-17 | Ethyl Corporation | Diesel fuels having anti-wear properties |
-
1984
- 1984-12-13 CA CA000470058A patent/CA1270642A/en not_active Expired - Fee Related
- 1984-12-28 EP EP84309143A patent/EP0147240B1/en not_active Expired
- 1984-12-28 EP EP87201461A patent/EP0251419B1/en not_active Expired
- 1984-12-28 EP EP87201460A patent/EP0247706B1/en not_active Expired
-
1990
- 1990-01-19 CA CA000615608A patent/CA1284583C/en not_active Expired - Fee Related
- 1990-01-19 CA CA000615609A patent/CA1284883C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0247706A3 (en) | 1988-01-13 |
| EP0147240A2 (en) | 1985-07-03 |
| EP0147240B1 (en) | 1989-04-05 |
| EP0247706A2 (en) | 1987-12-02 |
| EP0247706B1 (en) | 1989-06-14 |
| EP0147240A3 (en) | 1986-04-02 |
| EP0251419B1 (en) | 1989-05-31 |
| EP0251419A1 (en) | 1988-01-07 |
| CA1284883C (en) | 1991-06-18 |
| CA1284583C (en) | 1991-06-04 |
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| Date | Code | Title | Description |
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| MKLA | Lapsed |