FUEL COMPOUND FOR INTERNAL COMBUSTION ENGINES

Abstract: The invention concerns a fuel compound for use in hydrocarbon-fuel based internal combustion engines with spark ignition. The compound contains an anti-knock additive in the form of industrial ferrocene, specifically 0.001-0.2 wt.% α-hydroxyisopropyl/ferrocene.

Description: The present invention relates to lead compound free high-octane fuel compositions for internal combustion engines with spark ignition, prepared by using hydrocarbon fuels and anti-knock additive. There are known fuel compositions based on hydrocarbon fuels containing ferrocene derivatives as anti-knock additive such as m-nitrocinnamoyl ferrocene and o-chlorocinnamoyl ferrocene ( Toma,P.Ele ko, V.Vesely and M.Sali ova: Derivaty ferocenu ako prisady do benzinov. Acta Facultatis rerum naturalium universitatis comenianae-formatio et protectio naturae 1981 No. 7, 187-192 (Ref Journal CHEMISTRY, 12, II 224 (1982)) In addition, US-A-2810737 describes alpha-hydroxyalkyl ferrocene derivatives and their use as anti-knock agents in spark ignition fuels. A considerable obstacle for using ferrocene and its derivatives as an anti-knock additive to the engine fuels is that in the combustion chamber, more specifically on sparking plugs some deposits of iron oxides are formed, causing some failures in the operation of an engine (E.G. Perevalova, M.D. Reshetova, K.I. Granberg, "Methods of Elementorganic Chemistry", Moscow, Publishing House NAUKA, 1983, p. 439 (Russian edition)). In addition said m-nitrocinnamoylferrocene and o-chlorocinnamoylferocene are produced from ferrocene in a number of stages with a low yield and all characterized with a low solubility rate in the fuel composition. It is an object of the present invention to create a high octane fuel composition for internal combustion engines eliminating said drawbacks. Accordingly, the present invention provides a hydrocarbon based fuel composition suitable for spark ignition internal combustion engines, which comprises 0.001% - 0.02% by weight of Typically the hydrocarbon composition comprises: aromatic hydrocarbone 54 to 56 percent by weight. normal alkanes 12 to 13 percent by weight. isoalkanes 29 to 31 percent by weight. naphtheness 1 to 2 percent by weight. Such a composition has fractions as follows: initial boiling point: 60 grad.C distillation fraction of 10 percent; 83 grad.C distillation fraction of 50 percent: 114 grad.C distillation fraction of 90 percent: 156 grad.C distillation fraction of 96 percent: 190 grad.C density p20/4 being 0.7687 g/cm 3 and motor octane number being 80. The present invention further provides the use of as an anti-knock additive suitable for fuels. Examples and Comparative Examples The fuel composition octane number was determined on the plant UIT-85 by a motor method according to OMEA Standard 2243-80. The plug operation-to-failure time was determined on the single cylinder compartment of the engine ZIL-130 at alternative modes covering a wide spectrum of changed parameters such as temperature of cooling liquid, load, ingredients of mixture and lead angle of ignition. The test was carried out by some five-hour cycles. Iron oxide on the sparking plug A11 with an initial gap being 0.64 mm was appreciated by parameters as follows: change of sparking gap, change of the sparking plug weight, iron oxide deposit surface nature on the sparking plug electrodes. The sparking gap was measured by using the projector type SVET with magnification X100 and the iron oxide deposit surface nature was estimated by means of an optical microscope type MIN-8 with magnification X50. The fuel composition was tested by using, as anti-knock additive, a ferrocene derivative corresponding to the prior art (Nos 1. to 6 in the following Table) and a ferrocene derivative in different amounts according to the present invention (Nos. 7 to 10 in the following Table). No. Dosage of Additive Motor Octane Time Hour Increased Weight Spark gap Deposit on plug 1 m-nitro- 81.9 - - 640 Homogeneous cinnamoyl (1.9) 5 4 635 dense ferrocene 10 8 630 varnished 0.0296 15 13 625 deposit (0.00459) 20 16 605 25 24 595 30 33 580 35 40 560 40 50 525 45 stop 2 m-nitro- 81.6 - - 640 Homogeneous cinnamoyl (0.2) 5 0 640 dense ferrocene 10 2 635 varnished 0.0148 15 3 635 deposit (0.00229) 20 5 635 25 7 635 30 10 620 35 13 610 40 15 615 50 24 590 55 30 570 60 36 550 3 m-nitro- 80.2 - - 640 Homogenous cinnamoyl- (0.2) 5 0 640 dense ferrocene 10 2 640 varnished 0.00143 15 2 640 deposit (0.000229) 20 3 635 25 3 635 30 5 630 35 6 630 40 8 625 45 9 610 50 10 600 60 10 600 4 o-chloro- 81.8 - - 640 Homogeneous cinnamoyl- (1.8) 5 4 640 dense ferrocene 10 8 630 varnished 0.0287 15 12 620 deposit (0.00455) 20 17 600 25 27 590 30 32 580 35 40 570 40 55 550 45 58 490 50 stop 5 o-chloro- 81.7 - - 640 Homogeneous cinnamoyl- (0.9) 5 0 640 dense ferrocene 10 1 640 varnished 0.0144 15 2 640 deposit (0.00229) 20 4 635 25 7 635 30 9 630 35 14 620 40 16 600 45 21 590 50 28 570 60 38 540 6 o-chloro- 80.2 - - 640 Homogeneous cinnamoyl- (0.2) 5 0 640 dense ferrocene 10 2 640 varnished 0.00144 15 3 635 deposit (0.000229) 20 4 630 25 4 630 30 5 620 35 6 610 40 8 610 45 9 600 50 10 600 55 10 600 60 10 600 7 α-hydroxy- 82.0 - - 640 Crumbly microporous deposit isopropyl (2.0) 5 12 610 ferrocene 10 22 530 0.02 15 34 500 (0.00458) 20 40 450 25 55 400 30 52 410 35 52 415 40 55 400 45 50 410 50 50 415 55 54 400 60 51 410 8 α-hydroxy- 82.5 - - 640 Crumbly microporous deposit isopropyl- (2.5) 5 22 530 ferrocene 10 37 500 0.025 15 59 320 (0.00572) 20 68 320 25 68 320 30 72 310 35 stop 9 α-hydroxy- 81.1 - - 640 Crumbly isopropyl (1.8) 5 3 630 microporous ferrocene 10 7 620 deposit 0.01 15 11 590 (0.00229) 20 15 580 25 20 570 30 24 560 35 27 545 40 31 530 45 34 510 50 31 520 55 32 520 60 30 510 10 α-hydroxy- 80.3 - - 640 Crumbly isopropyl (0.3) 5 2 640 microporous ferrocene 10 2 640 deposit 0.001 15 3 640 (0.000229) 20 4 640 25 5 630 30 6 630 35 6 620 40 8 620 45 9 600 50 10 600 60 9 600 The data in the Table show that the iron oxide deposits formed on combustion of the fuel composition according to the invention and on combustion of the prior art fuel compositions have different natures, and that their accumulation on the sparking plug proceeds at different rates. Thus, the known prior art fuel produces dense solid varnished iron oxide deposits. However, on combustion of the fuel composition according to the present invention crumbly microporous deposits are formed. Thus, Examples 7 to 10 (fuel composition according to the invention) indicate that the accumulation of iron oxide deposits up to the equal weight state (50 to 55 mg) proceeds for 25 hours and remains at this level for a long period of the tests. At the same time the known prior art fuel composition containing an equivalent amount of iron (458 x 10 -5 percent by weight) in the fuel mixture when the similar amount of iron oxide deposit (50 to 55 mg) for a more extended period of time (35 to 40 hours) leads to a stoppage of the engine (see Examples 1,4). However, the step of decreasing the content of the anti-knock ferrocene additives by iron to 229 x 10 -5 percent by weight as for the fuel composition according to the invention increases the time to achieve the equal weight state of iron oxide deposit up to a level of 40 hours and to diminish the deposit value in the equal weight state down to 30 to 34 mg (see Example 9). At the same time, in the case of the known prior art fuel composition a similar amount of iron oxide deposit (30 to 34 mg) accumulates for 50 to 55 hours and for the next 5 to 10 hours a further increase of the iron oxide deposit occurs up to 35 to 38 mg. This feature shows that in the operation of the engine the iron oxide deposits will accumulate permanently. Thus, the use of α-hydroxyisopropyl ferrocene as an anti-knock additive serves to increase the life of sparking plugs without worsening the performances of the engine. In addition, the use of α-hydroxyisopropyl ferrocene in the fuel composition increases by 15 to 20 percent the growth of octane number as compared to m-nitrocinnamoylferrocene and o-chlorocinnamoyl ferrocene at the equivalent content of iron. The use of α-hydroxyisopropyl ferrocene increases by two times the content of iron as compared to the prior art fuel compositions containing m-nitrocinnamoylferrocene without inflicting any damage to the operation of sparking plug of the engine, increasing the octane number by 1.1 to 1.2 units (see Example 8). In addition the use of α-hydroxyisopropyl ferrocene reduces the toxicity rate of combustion products. The lower limit of the use of α-hydroxyisopropyl ferrocene is 0.001 percent (see Example 10),the upper limit is 0.02 percent (see Example 8) and corresponds to the maximum possible content at which a faultless operation of the engine is provided.

Claims: A hydrocarbon based fuel composition suitable for spark ignition internal combustion engines, which comprises 0.001 %0.02% by weight of A composition according to claim 1 wherein the fuel comprises 54-56% by weight of aromatic hydrocarbons, 12-13% by weight of normal alkanes, 29-31% by weight of isoalkanes and 1-2% by weight of naphthenes. A composition according to claim 1 or 2 wherein the fuel has an octane number of 80. Use of as an anti-knock additive suitable for fuels.

Inventors: BIRJUKOV FELIX IVANOVICH, DEMYANENKO EGOR ALEXANDROVICH, EMELYANOV VYACHESLAV EVGENIEVI, KARIBOV ALISKER KARIBOVICH, RADCHENKO EVGENY DMITRIEVICH, SACHIVKO ALEXEI VLADISLAVOVICH, TEMEROV SERGEI ANATOLIEVICH, TVERDOKHLEBOV VLADIMIR PAVLOVI, BIRJUKOV, FELIX IVANOVICH, DEMYANENKO, EGOR ALEXANDROVICH, EMELYANOV, VYACHESLAV EVGENIEVICH, KARIBOV, ALISKER KARIBOVICH, RADCHENKO, EVGENY DMITRIEVICH, SACHIVKO, ALEXEI VLADISLAVOVICH, TEMEROV, SERGEI ANATOLIEVICH, TVERDOKHLEBOV, VLADIMIR PAVLOVICH
Applicants: AKTSIONERNOE OBSCHESTVO ACHINS, AKTSIONERNOE OBSCHESTVO" ACHINSKY NEFTEPERERABATYVAJUSCHY ZAVOD"
Application year: 1993
Main classification: C10L1
IPC codes: C10L1