Fuel Compositions

Compression ignition fuel compositions and additive mixtures of organic nitrate ignition accelerator and C.sub.12-36 aliphatic hydrocarbyl succinimide or succinamide, in amounts sufficient to resist the coking tendencies of compression ignition fuel compositions when used in the operation of indirect injection diesel engines.

Throttling diesel nozzles have recently come into widespread use in indirect injection automotive and light-duty diesel truck engines, i.e., compression ignition engines in which the fuel is injected into and ignited in a prechamber or swirl chamber. In this way, the flame front proceeds from the prechamber into the larger compression chamber where the combustion is completed. Engines designed in this manner allow for quieter and smoother operation. The FIGURE of the Drawing illustrates the geometry of the typical throttling diesel nozzle (often referred to as the "pintle nozzle").

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 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 drilled orifice 14 in the injector body 16 and fill up to the seat 18. In severe cases, carbon builds up on the form 12 and the obturator 10 to such an extent that it interfers 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 ignition, decreased rate of fuel injection, increased rate of combustion chamber pressure rise, increased engine noise, and can also result in an excessive increase in emissions from the engine of unburned hydrocarbons.

While the composition of the low cetane number fuel 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.

In accordance with one of its embodiments, the invention provides distillate fuel for indirect injection compression ignition engines containing at least the combination of (i) organic nitrate ignition accelerator, and (ii) an additive selected from the group consisting of fuel-soluble C.sub.12-36 aliphatic hydrocarbon-substituted succinimide, C.sub.12-36 aliphatic hydrocarbon-substituted succinamide and mixtures thereof in which the aliphatic hydrocarbon group is derived from a linear .alpha.-olefin which has been isomerized to form a mixture of internal olefins, said combination being 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.

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 at least the combination of (i) organic nitrate ignition accelerator, and (ii) an additive selected from the group consisting of C.sub.12-36 aliphatic hydrocarbon-substituted succinimide, C.sub.12-36 aliphatic hydrocarbon-substituted succinamide and mixtures thereof in which the aliphatic hydrocarbon group is derived from a linear .alpha.-olefin which has been isomerized to form a mixture of internal olefins, said combination being present in an amount sufficient to minimize such coking in an engine operated on such fuel.

A feature of this invention is that the combination of additives utilized in its practice is capable of suppressing coking tendencies of fuels used to operate indirect injection compression ignition engines.

A wide variety of organic nitrate ignition accelerators 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-ethoxyethyl nitrate, 2-(2-ethoxy-ethoxy)ethyl nitrate, tetrahydrofurfuryl 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 C.sub.12-36 aliphatic hydrocarbyl succinimide or succinamide additives, component (ii) of the invention, can be made by conventional well-known procedures by reacting an olefin with maleic anhydride at elevated temperatures (e.g. 200.degree.-250.degree. C.) to form an alkenyl succinimide, which is reacted with ammonia (e.g. at 30.degree.-200.degree. C.) to form an alkenyl succinamide, alkenyl succinimide or mixtures thereof. Succinimide formation is favored at higher temperatures such as 150.degree.-200.degree. C.

The aliphatic substituent on the succinic group can be any aliphatic hydrocarbon group containing about 12-36 carbon atoms including alkyl, alkenyl and polyunsaturated hydrocarbon groups. Examples of the above additives include:

n-dodecenyl succinimide

1-methyltridecyl succinimide

2-ethyltetradecyl succinimide

n-hexadecenyl succinimide

n-octadecyl succinimide

n-octadecenyl succinimide

1-methyleiosyl succinimide

n-docosenyl succinimide

4-ethyltriacontyl succinimide

n-hexadecenyl succinimide

n-dodecenyl succinamide

2-ethyltetradecyl succinamide

n-octadecyl succinamide, and

n-octadecenyl succinamide.

In a preferred embodiment the aliphatic hydrocarbon group is bonded to the succinic group at a secondary carbon atom. These compounds have the formula: ##STR1## wherein n is a small integer from 2 to about 4 and Z is the group: ##STR2## wherein R.sub.1 and R.sub.2 are independently selected from the group consisting of branched and straight chain hydrocarbon groups containing 1 to about 34 carbon atoms such that the total number of carbon numbers in R.sub.1 and R.sub.2 is about 11-35. Examples of these additives are:

1-ethyltetradecyl succinimide

1-methylpentadecenyl succinimide

1,2-dimethyl octadecenyl succinamide

1-methyl-3-ethyl dodecenyl succinimide, and

1-decyl-2-methyl dotriacontyl succinimide.

In a highly preferred embodiment R.sub.1 and R.sub.2 are straight chain aliphatic hydrocarbon groups. These additives have improved solubility in distillate fuels. Examples of these additives are:

1-methylpentadecyl succinimide

1-propyltridecenyl succinimide

1-pentyltridecenyl succinimide

1-tridecylpentadecenyl succinimide, and

1-tetradecyleicosenyl succinimide.

The above highly preferred additives are made from .alpha.-olefins containing about 12-36 carbon atoms by isomerizing the .alpha.-olefins to form a mixture of internal olefins and reacting this mixture of internal olefins with maleic acid, anhydride or ester forming an intermediate and reacting the intermediate with ammonia to form amide, imide, or mixtures thereof. These .alpha.-olefins preferably contain a substantial amount of linear .alpha.-olefins. Additives made from isomerized .alpha.-olefins have greatly improved distillate fuel solubility compared with additives made with linear .alpha.-olefins. Thus, in the most preferred embodiment of the invention there is provided distillate fuel for indirect injection compression ignition engines containing at least the combination of (i) organic nitrate ignition accelerator and (ii) an additive selected from the group consisting of alkenyl substituted succinimide, alkenyl substituted succinamide and mixtures thereof wherein said alkenyl substituent contains about 12-36 carbon atoms, said additive being made by the process comprising (a) isomerizing the double bond of an .alpha.-olefin containing about 12-36 carbon atoms to obtain a mixture of internal olefins, (b) reacting said mixture of internal olefins with maleic acid, anhydride or ester to obtain an intermediate alkenyl substituted succinic acid, anhydride or ester, and (c) reacting said intermediate with ammonia to form a succinimide, succinamide or mixtures thereof said combination being present in an amount sufficient to minimize the coking characteristics of such fuel, especially throttling nozzle coking in the prechambers or swirl chambers of indirect injection compression ignition engines operated on such fuel.

Isomerization of the .alpha.-olefin can be carried out using conventional methods. One suitable method is to heat the .alpha.-olefin with an acidic catalyst. Especially useful acid catalysts are sulfonic acids such as methane or toluene sulfonic acid and the sulfonated styrene-divinylbenzene copolymers. Such catalysts are commercially available and are conventionally used as cation exchange resins. In the present method they are used in their acid form. Typical resins are Amberlyst 15, XN-1005 and XN-1010 (registered trademarks) available from Rohm and Haas Company. Use of such resins for isomerizing linear .alpha.-olefins is described in U.S. Pat. No. 4,108,889, incorporated herein by reference.

The hydrocarbyl succinimide and succinamide components of the invention should be used at a concentration of at least about 20 PTB (pounds per thousand barrels) to insure that the finished blend contains an adequate quantity of the foregoing ingredient although smaller amounts may be successfully employed.

The nitrate ignition accelerator, component (i), should be present in an amount of at least 100 to 1000 PTB (pounds per thousand barrels) of the base fuel. Preferably, the concentration of the ignition accelerator is about 400 to 600 PTB.

It is not believed that there is anything critical as regards the maximum amount of components (i) and (ii) 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 (i) and (ii) of the invention can be added to the fuels by any means known in the art for incorporating small quantities of additives into distillate fuels. Components (i) and (ii) 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 the hydrocarbyl succinimide or succinamide components of the invention. These additive fluid mixtures are added to distillate fuels. In other words, part of the present invention are coking inhibiting fluids which comprise organic nitrate ignition accelerator and the hydrocarbyl succinimide or succinamide additives described above.

Use of 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.

In these fluid compositions, the amount of components (i) and (ii) can vary widely. In general, the fluid compositions contain about 5 to 95% by weight of the organic nitrate ignition accelerator component and 5 to 95% by weight of the succinimide and/or succinamide components. Typically, from about 0.01% by weight up to about 1.0% by weight of the combination will be sufficient to provide good coking-inhibiting properties to the distillate fuel. A preferred distillate fuel composition contains from about 0.1 to about 0.5% by weight of the combination containing from about 25% to about 95% by weight of the organic nitrate ignition accelerator and from about 75% to about 5% by weight of the hydrocarbyl succinimide and/or succinamide components.

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 further embodiment of the invention is a distillate fuel additive fluid composition comprising (i) organic nitrate ignition accelerator, and (ii) an additive selected from the group consisting of alkenyl substituted succinimide, alkenyl substituted succinamide and mixtures thereof wherein said alkenyl substituent contains about 12-36 carbon atoms, said additive being made by the process comprising (a) isomerizing the double bond of an .alpha.-olefin containing about 12-36 carbon atoms to obtain a mixture of internal olefins, (b) reacting said mixture of internal olefins with maleic acid, anhydride or ester to obtain an intermediate alkenyl substituted succinic acid, anhydride or ester, and (c) reacting said intermediate with ammonia to form a succinimide, succinamide or mixture, said combination being present thereof in an amount sufficient to minimize the coking characteristics of such fuel, especially throttling nozzle coking in the prechambers or swirl chambers of indirect injection compression ignition engines operated on such fuel.

The method by which the succinimide and succinamide additives of the invention are made are illustrated by the following examples.

In a reaction vessel was placed 185 grams of octadecenyl succinic anhydride. This was melted by heating to 60.degree. C. and NH.sub.3 was injected. An exothermic reaction proceeded raising the temperature to 160.degree. C. After the reaction ceased the product was heated to 180.degree. C. under 29" Hg vacuum to remove volatiles. The product was octadecenyl succinimide.

In a reaction vessel was placed 1000 grams of linear .alpha.-octadecene. To this was added 187 grams Amberlyst 15 (5% moisture). The mixture was stirred under nitrogen and heated at 120.degree. C. for 3 hours. The isomerized product contained 3.6 wt % olefin dimer and the balance was internal C.sub.18 olefin. The product was separated from the resin.

In a second reaction vessel was placed 504 grams of the above isomerized C.sub.18 olefin and 300 ml heptane. The heptane was distilled out under vacuum to remove water. Then 2.4 grams of tri-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitylene stabilizer was added. The mixture was heated under nitrogen to 225.degree. C. Then 160 grams of molten maleic anhydride was slowly added over a 2.5-hour period. The mixture was stirred at 225.degree. C. for two more hours and then unreacted maleic anhydride was distilled out by pulling vacuum to 30" Hg while holding the reaction mixture at 200.degree. C. The product was principally secondary C.sub.18 alkenyl succinic anhydride.

In a separate reaction vessel was placed 532.5 grams of the above isomerized octadecenyl succinic anhydride. This was heated under nitrogen to 165.degree. C. and then ammonia was injected causing the temperature to rise to 180.degree. C. Ammonia injection was continued until exotherm stopped. The mixture was heated at 170.degree. C. under vacuum to remove water yielding isomerized octadecenyl succinimide.

In a reaction vessel was placed 1005 grams of linear .alpha.-eicosene and 187 grams of Amberlyst 15 (5% moisture). The mixture was heated under nitrogen at 110.degree.-125.degree. C. for 6 hours. The product was internally unsaturated eicosene containing 3.3% eicosene dimer.

In a separate reaction vessel was placed 560 grams of the above isomerized eicosene and 200 ml heptane. The heptane was distilled out to dry the eicosene. At 140.degree. C., 3.1 grams of tri-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitylene stabilizer was added and the mixture heated to 210.degree. C. Over a 2.5-hour period, 156.8 grams of maleic anhydride was added to about 225.degree. C. Following this unreacted maleic anhydride was distilled out under vacuum at 210.degree. C. leaving isomerized eicosenyl succinic anhydride.

In another reaction vessel was placed 570 grams of the above isomerized eicosenyl succinic anhydride. This was heated to 160.degree. C. and ammonia injection started. The temperature rose to 175.degree. C. Ammonia injection was continued at 175.degree. C. until the temperature dropped. Then 30" Hg vacuum was slowly applied to distill out water and ammonia. Additional ammonia was injected to be sure no anhydride remained. There was no further reaction so this ammonia was stripped out at 30" Hg vacuum at 170.degree. C. yielding isomerized eicosenyl succinimide.

In a reaction vessel was placed 1100 grams of linear C.sub.16 -C.sub.18 .alpha.-olefin mixture. The olefin mixture was isomerized following the procedure in Example 3.

In a separate vessel was placed 485 grams (2 moles) of the above isomerized olefin. This was heated at 100.degree. C. under 30" Hg vacuum to remove water. To it was then added 2.4 grams tri-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitylene. The mixture was heated under nitrogen to 225.degree. C. and then 152 grams of molten maleic anhydride was added over a 3-hour period. The mixture was stirred 30 minutes at 225.degree. C. and an additional 50 grams of maleic anhydride was added. This mixture was stirred 30 minutes at 225.degree. C. following which unreacted maleic anhydride was distilled out at 200.degree. C. under 30" Hg vacuum.

In a separate reaction vessel was placed 598 grams of the above isomerized C.sub.16 -C.sub.18 alkenyl succinic anhydride. Ammonia injection was started at 140.degree. C. raising the temperature to 145.degree. C. Ammonia injection was continued at 130.degree. C. until no further ammonia was absorbed. The mixture was then heated to 180.degree. C. to distill out water and ammonia yielding isomerized C.sub.16 -C.sub.18 alkenyl succinimide.

In order to determine the effect of the fuel compositions of the present invention on the coking tendencies of diesel injectors in indirect injection compression ignition engines, use was made of a diesel fuel injector test apparatus developed for the purpose of screening chemical agents for use as anticoking, antideposit and antivarnish agents. The design of the apparatus allows it to accommodate any type of conventional automotive diesel fuel injector used in diesel engines such as the Bosch injectors used in turbocharged XD2S engines and the Lucus pencil-type or mini-fuel injectors used in 6.2 liter or 350 cu. in. diesel engines. The apparatus comprises a diesel fuel injector nozzle assembly attached to and extending into an aluminum cylinder 2.5 inches in width and 5.0 inches in diameter. Attached to and extending into the opposite side of the aluminum block is a 1-inch pipe assembly consisting of a connector nipple and tee which acts as a combustion chamber into which diesel fuel is injected by the injector assembly. The chamber is coupled to a flash arrestor and exhaust-gas assembly. Also coupled to the combustion chamber is a serpentine-gas/air heater, 0.5 inches in diameter and 6.5 inches in length. The heater controls the temperature of the air entering the combustion chamber. If desired, air temperatures up to 750.degree. C. can be produced. Under normal testing conditions, air temperature is maintained at a range between about 470.degree. C. and 525.degree. C.

Air flow rate, which is critical to the operation and replication of the test, is maintained by a mass flow controller to within 0.1 liter per minute at flow volumes of 20 to 50 liters per minute. A standard single cylinder diesel engine Bosch fuel pump is used to develop pressure and fuel volume passing into the injector. A 1-horsepower motor directly connected to the fuel pump is operated at 1750 RPM providing approximately 875 injections of fuel per minute. The fuel pump can be adjusted to provide fuel flow rates ranging from 35 milliliters to 3000 milliliters per hour. Standard operating fuel flow rates used for testing generally range between about 80 and 120 milliliters per hour. Under the standard operating conditions of air flow and fuel flow, incipient combustion of injected fuel occurs. Tests are carried out using 1-quart samples of fuel, with or without additives. The length of each test is four hours. After the test operation, the injectors are carefully removed from the apparatus so as not to disturb the deposits formed thereon.

After the test, the amount of deposit, coke or varnish on various areas of the injector external or internal parts are rated. Visual differences in amounts of deposits between a non-additive test and one with an additive are used to distinguish and establish the effect of the chemical agent being tested as an anticoking additive. The areas of the injector parts which are rated for deposits include (i) the external area of the nozzle face, (ii) an area around the injector orifice extending one millimeter in diameter from the center of the orifice, (iii) the rim of the nozzle orifice, (iv) the exterior pintle tip, (v) the pintle obturator, and (vi) the nozzle face.

To demonstrate the anticoking effects of the present additives, a base fuel was prepared consisting of a commercially available diesel fuel having a nominal cetane rating of 37. FIA analysis indicated that the fuel was composed by volume of 41% aromatics, 2.0% olefins and 57% saturates. The base fuel also contained 140 pounds per thousand barrels (PTB) of mixed octyl nitrates (a commercial product available from Ethyl Corporation under the designation DII-3 Ignition Improver).

A test blend was prepared from this base fuel and was designated Fuel A. Fuel A contained, in addition to 140 PTB of mixed octyl nitrates, 50 PTB of the isomerized eicosenyl succinimide additive of Example 4.

The diesel fuel injection test apparatus was operated for four hours on the base fuel followed by operation for four hours on the test blend (1-quart samples of each). Operating conditions for all tests were as follows:

Before each test, a new Bosch DNOSD-251 nozzle was installed in the apparatus.

After the tests, the injectors were carefully removed from the apparatus so as not to disturb the deposits formed thereon. Visual ratings of injector deposits were made with a deposit rating system in which 1=clean and 5=extreme deposit build-up.

The test results are given in Table I below:

The results presented in Table I indicate less coking deposits with Fuel A as compared to the Base Fuel.