EP0629686B1 - Fuel compound for internal combustion engines - Google Patents

Fuel compound for internal combustion engines Download PDF

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Publication number
EP0629686B1
EP0629686B1 EP94900321A EP94900321A EP0629686B1 EP 0629686 B1 EP0629686 B1 EP 0629686B1 EP 94900321 A EP94900321 A EP 94900321A EP 94900321 A EP94900321 A EP 94900321A EP 0629686 B1 EP0629686 B1 EP 0629686B1
Authority
EP
European Patent Office
Prior art keywords
ferrocene
weight
fuel
internal combustion
deposit
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP94900321A
Other languages
German (de)
French (fr)
Other versions
EP0629686A4 (en
EP0629686A1 (en
Inventor
Egor Alexandrovich Demyanenko
Felix Ivanovich Birjukov
Alisker Karibovich Karibov
Alexei Vladislavovich Sachivko
Sergei Anatolievich Temerov
Vladimir Pavlovich Tverdokhlebov
Vyacheslav Evgenievich Emelyanov
Evgeny Dmitrievich Radchenko
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AKTSIONERNOE OBSCHESTVO" ACHINSKY NEFTEPERERABATYVAJUSCHY ZAVOD"
Original Assignee
AKTSIONERNOE OBSCHESTVO" ACHINSKY NEFTEPERERABATYVAJUSCHY ZAVOD"
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Publication date
Application filed by AKTSIONERNOE OBSCHESTVO" ACHINSKY NEFTEPERERABATYVAJUSCHY ZAVOD" filed Critical AKTSIONERNOE OBSCHESTVO" ACHINSKY NEFTEPERERABATYVAJUSCHY ZAVOD"
Priority claimed from PCT/RU1993/000239 external-priority patent/WO1994009091A1/en
Publication of EP0629686A1 publication Critical patent/EP0629686A1/en
Publication of EP0629686A4 publication Critical patent/EP0629686A4/xx
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Classifications

    • 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
    • C10L1/30—Organic compounds compounds not mentioned before (complexes)
    • C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)

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.% alpha -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
Figure 00010001
and o-chlorocinnamoyl ferrocene
Figure 00010002
(
Figure 00010003
Toma,P.Ele
Figure 00010004
ko, V.Vesely and M.Sali
Figure 00010005
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
Figure 00030001
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/cm3 and motor octane number being 80.
The present invention further provides the use of
Figure 00030002
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 (4)

  1. A hydrocarbon based fuel composition suitable for spark ignition internal combustion engines, which comprises 0.001 %0.02% by weight of
    Figure 00100001
  2. 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.
  3. A composition according to claim 1 or 2 wherein the fuel has an octane number of 80.
  4. Use of
    Figure 00100002
    as an anti-knock additive suitable for fuels.
EP94900321A 1992-10-22 1993-10-20 Fuel compound for internal combustion engines Expired - Lifetime EP0629686B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
RU92001874/04A RU2019559C1 (en) 1992-10-22 1992-10-22 Fuel composition
RU9201874 1992-10-22
PCT/RU1993/000239 WO1994009091A1 (en) 1992-10-22 1993-10-20 Fuel compound for internal combustion engines

Publications (3)

Publication Number Publication Date
EP0629686A1 EP0629686A1 (en) 1994-12-21
EP0629686A4 EP0629686A4 (en) 1995-01-04
EP0629686B1 true EP0629686B1 (en) 1998-07-22

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP94900321A Expired - Lifetime EP0629686B1 (en) 1992-10-22 1993-10-20 Fuel compound for internal combustion engines

Country Status (2)

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EP (1) EP0629686B1 (en)
RU (1) RU2019559C1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014165950A1 (en) * 2013-04-10 2014-10-16 Firmano Lino Junior Non-deposit forming catalytic additive for additive oil cracking, and for fuel octane increase and combustion

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2810737A (en) * 1953-07-01 1957-10-22 Du Pont Dicyclopentadienyl group viii metal compounds having an alpha-hydroxyalkyl substituent on one or both of the cyclopentadienyl rings
FR1140411A (en) * 1954-11-22 1957-07-22 Gulf Research Development Co Organic hydrocarbon composition containing a metallo-cyclopentadienyl
US3377248A (en) * 1965-10-07 1968-04-09 Colgate Palmolive Co Methods and compositions of ferrocene cyclic ethers in the treatment of iron deficiency anemia
RU2006497C1 (en) * 1992-04-01 1994-01-30 Темеров Сергей Анатольевич METHOD OF ( α-HYDROXYISOPROPYL) FERROCENE SYNTHESIS

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EP0629686A4 (en) 1995-01-04
RU2019559C1 (en) 1994-09-15
EP0629686A1 (en) 1994-12-21

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