DE1420936A1 - Leaded gasoline composition - Google Patents

Description

Leaded gasoline composition

The invention relates to improved SiOH kotortreibstoffzusammensetzungen with increased octane properties ₀

According to the invention there is an improved gasoline fuel Composition of higher octane value created, which is about $ 3 to $ 65! ethylbenzene with 1 to 4 methy! groups and 0.132 to 1.585 g / liter of lead as an anti-knock agent in the form of tetramethyl lead alone or in a mixture with incidentally Contains a maximum of 75 other alkyl lead compounds. Generally Speaking of which there are two different types of mixture used in accordance with the invention, both under certain conditions of use are particularly advantageous. The first variety can be considered a "physical" mixture of pure Alkyl lead compounds with methyl or ethyl as alkyl groups are designated. For example, tetraalkyl lead anti-knock mixtures are used, which are obtained by simply mixing 3much tetraethyl lead and Letramethyl lead are obtained that the alkyl groups each half consist of ethyl and methyl. In the same sense, similar, physical mixtures of., Te tr aä thy 1-lead and tetramethyl lead in such proportions "that either the alkyl groups to 25 $ from ethyl and 75 $ from methyl or 7596 from ethyl and are methyl at $ 25,

8 09801/0359 -2-

In a similar way, purely physical mixing and blending according to the invention can be used Manufacture anti-knock agents in which the proportion of ethyl radicals varies between $ 0 and $ 75. The amount of ethyl radicals can still a little over $ 75, but always have to at least 25 weight percent tetramethyl lead may be present; mixed alkyl lead compounds include physical mixtures from tetraethyl lead, tetramethyl lead and organic lead compounds that contain both ethyl and methyl radicals in the molecule contain. Such a mixture consists for example of 34 $ of tetraethyl lead, 34 $ of tetramethyl lead and of $ 32 from diethyldimethyl lead. Similarly, as Anti-knock agent is a physical mixture of tetraalkyl lead compounds are used where durohweg ethyl and methyl radicals are attached to the lead atom. Which also includes for example a physical mixture of 50 $ methyl triethyl lead and 50 $ trimethylethyl lead ','

According to the invention, mixtures of alkyl lead compounds are also used used, which arise from radical rearrangement between tetramethyl lead and tetraethyl lead. If those two alkyl lead compounds in the presence of a catalyst, for example an aluminum halide, such as aluminum umohloride, of an alkyl aluminum halide such as ethyl aluminum sesquihalide or an alkyl lead halide such as triethyl lead chloride etc., are mixed with one another, a rearrangement reaction occurs in which all five are possible Tetraalkyl lead compounds in proportions corresponding to an arbitrary distribution of methyl and ethyl radicals

-3-80980 1/0359

H20936

are present between the lead atoms. So if you start from an equimolar mixture of 8 moles of tetraethyl lead and treat it with aluminum chloride until equilibrium is reached, a mixture of about 1 mole of tetramethyl lead, 4 moles of trimethylethyl lead, 6 moles of dimethyl diethyl lead, 4 moles of methyltriethyl lead and 1 mole of tetraethyl lead is obtained.

Such misalignments resulting from an equilibrium rearrangement of methyl and ethyl radicals are hereinafter referred to as "chemical" mixtures. Their main effect is that x ± "about 25 to about 75% of the alkyl groups consist of methyl and the remainder of ethyl". They contain about C _; 4 to about 40 moles of tetramethyl lead, about 4.7 to about 40 moles of ethyl trimethyl lead, about 21 to about 37.5 moles of ethyl methyl lead, about 2.5 to about 42 moles of trimethyl ether and about 0.2 to about 31.6 mol $ tetramethyl lead, the following special exemplary embodiments are listed: A 25-75 $ mixture of - by weight - 0.4 $ tetramethyl lead, 4.3 $ ethyltrimethyl lead, 20.2 $ diethyldimethyl lead, 42.1 $ triethyimethyl lead and 33 $ tetraethyl lead, in which the alkyl groups consist of 25 $ methyl and the rest of ethyl, a 50: 50 $ mixture with 50 $ ixethyl and 50 $ ethyl radicals - also by weight - 5.7 $ tetramethyl lead, 23.8 $ ethyltrimethyl lead, 37.4 $ diethyldimethyl lead, 26.2 $ triethylmethyl lead and 6.9 $ tetraethyl lead and a 75:25 mixture in which 75 $ of the alkyl groups are methyl and the remainder of them consists of ethyl, with parts by weight of tetramethyl lead, 42.1 $ ethyltrimethyl lead, 22.2 $

BATH

8 U 9 δ U 1 / U 3 5 9

Diethyldimethyl lead, 5.296 triethylmethyl lead and 0.5-6 Tetraethyl lead.

The fuel compositions according to the invention show remarkably better octane properties. Furthermore the inventive finding was made that with a fuel that contains certain special aromatics, through the use of the aforementioned lead anti-knock agents, extraordinarily high and surprising octane improvements can be achieved. When adding tetramethyl lead to such fuels, the octane improvements are many larger than they can be achieved by the same amount of lead in the form of tetraethyl lead. Contains the invention the basic fuel is about $ 3 to about $ 65 more certain, below described aromatics and also about 0.132 to 1.585 g / liter of lead in the form of a lead compound above specified type.

The fuels that can be used in the fuels according to the invention Aromatics are Beneoley, those with 1 to 4 methyl groups are substituted. These include methylbenzene (toluene), the 1,2-, 1,3- and 1,4-isomers of dimethyl benzene, namely 0-, m- and p-2ylenes, the 1,2,3-, 1,2,4- and 1,3,5-isomers of trimethylbenzene and the 1,2,3,4-, l, 2,3, f and 1,2,4,5 isomers of tetramethylbenzene. Studies have shown that the octane improvements achieved are particularly pronounced when benzenes with a higher degree of methyl substitution are used * those obtained by using the lead compounds according to the invention The improvements achieved are therefore with xylölhaltige

8 0 9 0 0 1/0359 .. "" * "

Fuels stronger than those containing toluene and amplify further if the aromatic consists of trimethylbenzene · Therefore, fuels are preferably used in which the methylbenzene component consists at least partially of polymethylbenzenes with up to 4 methyl groups.

An explanation of this surprising behavior in relation to the compositions improved according to the invention Rapid tapping cannot be given at the moment. Prefer fuels containing methyl substituted benzenes the lead compounds according to the invention, while Benzenes with all other hydrocarbon groups are substituted, prefer the addition of tetraethyl lead,

There are two well-known laboratory tests, namely the "Research Method" according to ASTM D 908-55 and the "Motor Method" according to ASTM D 357-56, which are used as a measure of fuel performance in a multi-cylinder engine. umstesten and the. Performance in a real vehicle has been the subject of much recent research »These include the lectures given by E" Β »Corner on" Octanes from Laboratory to Road "at the Society of Automotive Engineers' meeting in Atlantic, New Jersey, in the summer of 1956, by Yi.E ₀ Morris on "Correlations Between Road Octanes, Laboratory Octenes, and Hydrocarbon Type" at the Society of Automotive Engineers meeting. iiational -Fuels: and Lubricants inlfov, ömfeer 5.1956., by Y / arren USW. about "MatcMögi ^: 9asöline Axifcikn © bk £ _r Prop € rties..ando βχίϊ Future -Engines * · '-'&& £ dem! 'reffen der Division- Ό-f. Refining ^

BATH ORIGINAL

80 900 1/0350 ':;^; _k : .. · J · ^

U29936

dee American Petroleum Institute in May 1957. These authors have drawn the conclusion from many empirical studies that the Research Method Test has the slow-running anti-knock properties of a fuel in a multi-cylinder engine during the engine metirod test a measure of the anti-knock efficiency of a fuel in an engine at high speed.

Even though an increase in the research octane number is desirable to ensure good low-speed performance however, as already mentioned, the problem of sonar tapping is of particular importance in modern automobiles. Create the compositions of the invention Now not just slow speed improvements, but are special suitable for high speed conditions.

The higher octane performances can be seen from the tests below. A series of special aromatics were each mixed with 40 $ "40 octane number primary reference fuel ¹¹ , which consists of 40 $ isooctane and 60 $ n-heptane and forms a member of the series of primary reference fuels used as the standard for octane measurements. The use of such primary reference fuels is known in the Faohwe.lt.

Each of $ 40 primary reference fuel and $ 60 one The mixture containing specific aromatics was divided into five portions. One serving remained unchanged. One second and third servings were 0.277 and 0.837 g / liter, respectively Lead in the form of tetraethyl lead and the fourth and fifth parts were 0.277 and respectively. 0.837 g / liter of lead in the form various lead compounds according to the invention added.

809801/0359 _BAD ORIGINAL _ _{? -}

This procedure was repeated with a large number of special aromatic compounds, and for each mixture Research and engine octane number "were determined. In this way, octane numbers for a lead-free mixture, for Mixtures with 0.277 g / Ed ^ r lead and for those with 0.837g / Iiiter of lead received. The octane improvements brought about by the same amounts of lead once in the form of tetraethyl lead and on the other hand in the form of various lead compounds according to the invention are in the following Tables compared with one another, of which Table I those obtained by the research method and Table II the Show the performance determined with the Motor-Method when using tetramethyl lead.

9801/0359

CD CO CD

° Aromat +

^ 4O56 octane number

^ ¹ "Primary benefits

"*" * fuel

benzene

Ethylbenzene iaopropylbenzene n-butylbenzene secondary butylbenzene Tertiary butylbenzol Diethylbenzene triethylbenzene diisopropylbenzene

Methylbenzene 1,2-dimethylbenzene. 1,3-dimethylbenzene 1,4-dimethylbenzene 1,2,4-trimethyl benzene

* TMB = tetramethyl lead ♦♦ TAB = tetraethyl lead

I. Beeearch * octane number ffahl τη j tf Tetram · «·
thylblei
Profit on
OktaYi number 1 98.0
90.3
99.4
99.6.
95.5 -1.0
-0.7
-0.2
0.0
-0.8 • Octane number with
0.837 g / liter
Lead in lorm
from TAB** < octane g / liiter
in shape Medium -0.5 TMB * 98.1
102.4
104.1
94.0
99.7
102.3
102.6
99.6
103.6 3 0.277
lead
from IAB ** -2.4
-1.6
-1.9
-3.9
-1.6
-2.1
-2.0
-2.8
-2.2 96.8
101.4
103.1
90.8
99.3
101.5
101.6
98.8
102.4 cc
O
O T i TBIB * 89.9
98.8
101.1
86.3
95.5
98.9
99.0
95.2
99.8 Medium -2.3 101.2
93.1
102.3
102.3
97.6 CQ 87.5
97.2
99.2
82.4
93.9
96.8
97.0
92.4
97.6 101.4
94.1
102.6
102 ·, 5
98.3 Tetrams
thylblei
Profit on
Octane number a b e 1 1 e Oktanverbeeaeruneen of inventive fuels 97.0
89.6
99.2
99.6
94.7 -1.3
-1.0
-1.0
-3.2
-0.4
-0.8
-1.2
-0.8
-1.2 Mean -1.2 octane
number
clear +0.2
+1.0
+0.3
..- +0.2
'+0.7 Mean +0.5 80.0
91.6
84.3
76.0
87.9
91.5
91.7
87.0
92.7 LO
CO
O O
CO 91.6
88.0
95.5
95.4
93.1 •

T a b e lie

II

Aromat + Octane improvements of fuels according to the invention Engine octane number g / liter Tetrams 85.8 +0.2 Ok tan • fiahl with Tetram co $ 40 octane Octane number with in shape thylblei 78.3 0.0 0.837 g / liter thylblei σ> Primary reference 0.277 Profit on 92.0 +1.1 lead in shape Profit on ο
CNJ fuel lead TAB** Octane number • 88.9 +0.5 from Octane number <f octane from 8'3.6 86.8 +0.2 TMB * ,TAB** * "* benzene number TMB * 91.7 -0.5 Mean +0.4 88.6 89.1 -0.5 Ethylbenzene clear 83.1 93.1 -3.1 93.3 94.0 -0.7 Ieopropylbenzene 88.6 85.4 -1.8 95.6 96.8 -1.2 n-Buty! benzene 72.6 91.3 91.7 -3.0 88.7 90.9 -2.2 Secondary butylbenzene oil 82.4 82.4 93.4 -0.7 96.8 96.8 0.0 Tertiary butylbenzene 86.0 91.0 91.1 -0.9 96.5 98.6 -2.1 Diethylbenzene 73.5 92.5 89.7 -1.1 94.4 96.1 -1.7 Triethylbenzene 82.3 90.0 95.5 -0.9 93.7 94.2 -0.5 Diisopropylbenzene 85.8 88.8 -0.8 95.5 95.5 '0.0 84.4 94.7 Mean -1.4 Mean -1.0 Methylbenzene 82.3 91.5 90.8 +0.7 1,2-dimethylbenzene 87.2 86.0 83.9 82.0 +1.9 1,3-dimethylbenzene 78.3 98.8 97.2 +1.6 1,4-dimethylbenzene 80.8 93.1 97.4 96.2 +1.2 1,2,4-trimethylbenzene 76.1 90.4 92.0 89.2 +2.8 86.9 87.0 • Mean +1.6 85.8 cn
LD
OO 83.8 9801/0 * TMB «tetramethyl lead ** TAB = - tetraethyl lead

The first nine mixes listed in the table each contain an aromatic which does not dung-worthy heard. - Show at all nine! Fuels both Eesearoh and Motor rMethod that the one with Tetraätnylblei Octane enhancements achieved that with tetramethyl lead are superior to both the 0.277 and 0.837 g / liter lead levels. In striking contrast are the fuel compositions according to the invention, in which the aromatic compound of toluene, o-, m- or p-xylene or Srime thyIbenzol, surprisingly and unexpectedly the octane improvements achieved with tetramethyl lead in the fuel are generally higher than that with tetraethyl lead created. The only exception to this general cone is only made by the Research Method bruises Mixtures with 0.277 g / liter of lead, in which sioh shows a slight tetraethyl lead advantage. But even in this case it is when tetramethyl lead is used in the fuel eriohtlioherweise more advantageous if this the inventive, contains aromatic components. While the average advantage of the tetraethyl lead over the tetramethyl lead for fuels with other aromatics than the 2.3 octane number units according to the invention, went this superiority in fuels with a content of aromatic constituents according to the invention to only nooh 0.5 units back. At the 0.837 g / liter lead level For other fuels, the use of tetraethyl lead resulted in a research octane number advantage of 1,2, while in direct contrast to it

80980 1/0359

-11-

According to the invention, the advantage of propellants was completely reversed and tetramethyl lead was superior by an average of 0.5 research octane numbers. Bine Nooh conspicuous and higher superiority of tetramethyl lead show the Motor Method Ergebnlsee. At the 0.277 g / liter lead content level, other propellants, that are not in accordance with the invention, showed a mean superiority of 1.4 octane units.

Tables III and IV give the results of the Research method and Tables V and VI those of the Motor method again.

-12-

809801/0359

Tabel

III

Aromat +

40 # octane number

Primary reference

fuel

benzene

Ethylbenzene

Isopropylbenzene

Secondary butylbenzene

Tertiary butylbenzene

Triethylbenzene

Diisopropybenzene

Methylbenzene
1,2-dimethylbenzene
1,3-dimethylbenzene
1,4-dimethylbenzene
1,2,4-trimethylbenzene
1,3 »5-trimethylbenzene

Oktanverbeaaerungen of erfindungagemäasen propellants

Beaearch octane number

Clear octane number

82.0 94.0 91.0 90.2 92.2 81.6 96.0

92.2 88.4 97.3 96.2 94.6 97.4

Mix 0 B. , 277 "/ liter lead ala Mix D TAB Medium Anti 90 2 Mix C 89.8 90.0 knock advantage 100, 6th 89.6 100.2 100.1 the invention 98 7th 100.0 98.2 98.9 opposite TAB 97 7th 97.6 97.1 97.4 99 4th 96.8 99.2 99.3 -0.1 Octane number with 89 3 98.7 88.5 90.2 +0.3 Mix A 102, 2 88.2 102.0 102.0 -0.5 90.4 101.7 -0.1 100.4 98 2 97.6 97.9 -0.1 99.2 91 6th 97.7 91.6 91.9 -1.2 97.7 101, 8th 91.3 101.4 101.4 OtO S 99.6 101, 3 101.6 100.8 100.9 Medium -0.3 ^ 90.2 97 1 100.8 96.9 96.8 0.0 ο 102.1 102, 0 96.5 101.8 101.7 -0.1 co 101.8 +0.2 ο 98.2 +0.1 ο 91.9 0.0 = ° 101.7 +0.1 101.2 96.8 101.8

Mean +0.1

Mix A = "Chemical mixture" from the equilibrium storage reaction of

TAB
Mix B = "Cfcemiache mixture" from the equilibrium rearrangement reaction of 50 mol

TAB
Mix C = "chemical mixture" from the equilibrium transfer reaction of 75 mol

TAB
Mix D = "Phyaikaliache Mixture" of 50 Mol- # TMB and 50 Mol ~ # TAB

TUB and 75 Mol-96 TMB and 50 Mo 1-5 *

-56 TMB and 25 Mon 1-9 »

Table IV

CD CO CD O CM

Aromat + $ 40 octane primary reference fuel

Benzene Ethylbenzene Isopropylbenzene Secondary butylbenzene Tertiary butylbenzene triethybenzene diisopropylbenzene

Methylbenzene 1,2-dimethylbenzene 1,3-dimethylbenzene 1,4-dimethylbenzene oil

1,2,4-trimethylbenzene 1,3,5-trimethyl benzene

Octane improvements of fuels according to the invention Research octane number Mix B 837 g / liter lead as Mix D TAB Medium Anti 97.6 Mix C 97.2 97.2 knock advantage 104.3 97.4 103.8 103.8 the invention octane 103.0 104.3 102.7 102.9 opposite TAB number 101.7 103.0 101.2 101.1 clear 103.8 101.6 103.3 103.8 +0.2 96.1 103.6 95.5 96.0 +0.3 82.0 Octane number with O, 107.0 95.7 106.0 106.0 0.0 94.0 Mix A 106.3 +0.4 91.0 97.5 102.0 101.2 101.4 -0.2 cn 90.2 104.0 95.2 101.8 94.6 94.4 -0.1 in 92.2 103.1 104.8 95.4 104.4 104.3 +0.5 ^ 81.6 101.5 .104.3 104.9 104.0 104.0 Mean +0.2 - ^ 96.0. 103.9 99.5 104.4 99.5 99.2 96.1 104.8 99.9 104.4 104.2 +0.6 S. 92.2 106.6 105.0 +0.3 co 88.4 +0.2 97.3 101.7 +0.4 96.2 94.8 +0.5 94.6 104.5 97.4 104.2 99.3 104.6

Mean +0.4

Mixtures A through D are the same as in Table III

HHHHHB

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Φ Φ O O

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VD CO VD VD VD VD OD

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H-cf Φ 4

to H Φ

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Pd: η co

f3 4 Φ H * σ ¹ CO

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οοοοοο νηνη HVDVJi H

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80 980 1/0359 _{ORieiNAL1NSpE0TE0}

η PK

Q φ μ

η 4 ο φ «ϋ

P teJHi FJ: 4 <* σΉΟ ro H-4 P cf P ^ Φ HC Η ·> {3 H

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Aromat + $ 40 octane primary purchase fuel

benzene

Ethylbenzene Isopropylbenzene Secondary butylbenzol Tertiary butylbenzene Diisopropybenzene

ethylbenzene 1,2-dimethylbenzene 1,3 ~ dimethylbenzene 1,4-dimethyl benzene 1,2,4-trimethyl benzene If315-trimethylbenzene

le VI Engine octane number Mix B , 837 s / liter Lead as TAB Medium Anti iT> T a b e 1 88.0 Mix C Mix D 88.0 knock advantage LO
CO
CD 94.2 88.0 88.0 94.1 the invention Octane improvements of fuels according to the invention 96.7 94.2 94.2 96.8 opposite TAB O
CO Octane number with O, 95.6 96.5 96.5 96.4 O Mix A 97.4 95.6 95.4 97.8 0.0 O octane 88.1 100.4 97.2 97.0 100.7 +0.1 CX) number 94.1 100.3 100.4 -0.2 clear 96.8 91.7 91.2 -0.6 96.0 85.0 92.0 91.6 83.5 -0.2 74.0 97.8 95.9 85.8 84.9 95.7 -0.3 85.1 100.6 94.8 96.4 96.4 94.4 Medium -0.2 85.1 89.8 95.0 94.8 89.1 +0.4 85.4 91.3 96.6 90.8 90.0 96.5 +1.3 86.0 83.6 98.6 97.4 +0.4 89.3 95.8 +0.4 94.5 +0.9 82.0 89.4 +0.7 78.6 96.2 86.3 85.0 84.3 87.8

Mean +0.7

The hybrids A to D are the same as in Table III

The first seven listed in Tables III through VI Mixtures all contain an aromatic, the does not belong to the class of the inventive. For all seven fuels, both research and engine methods show that those with anti-knock agents according to the invention The octane improvements achieved are practically the same as when using tetraethyl lead, and that is the case for both the 0.277 and 0.837 g / diter lead levels. In the case of fuels according to the invention, there is a striking contrast to their aromatic constituent So from toluene, ο-, m- or p-xylene or trimethylbenzene consists, surprisingly and unexpectedly, the octane improvements that are achieved when using inventive Anti-knock agents are achieved in the fuels, on average greater than those achieved with tetraethyl lead additive. The superiority of the anti-knock agents according to the invention over tetraethyl lead is not so pronounced here as in Table I, but even here the difference is between the hydrocarbons of the invention and the other hydrocarbons are clearly recognizable. Also, the difference in relative effectiveness is the claimed anti-knock compounds in comparison to tetraethyl lead in the two types of fuel.

It is true that massive amounts of tetramethyl lead can be used make significant improvements, but the greatest and most important improvements come from use from about 0.660 to 0.925 g / liter. This is noticeable by the kotor-kethod values on propellants

809801/0359 ORIGINAL INSPECTED

-17-

Proven of 837 g / liter of lead. While tetraethyl lead showed a superiority of 1.0 octane number units with fuels not according to the invention, the advantage was clearly reversed as soon as the aromatic component consisted of toluene, a xylene or trimethylbenzene * With these aromatic components, tetramethyl lead showed an average advantage of 1 over tetraethyl lead 6 octane units. These results were even more striking when viewed on a bin basis. At the 0.837 g / liter lead content level, the use of aromatic components such as n-butylbenzene, tertiary butylbenzene or diethylbenzene (all of which are outside the scope of the invention) resulted in a tetraethyl lead advantage of over 1.5 engine octane numbers. But as soon as these aromatic hydrocarbons were replaced by components such as o-, m- or p-xylenes, surprisingly and contrary to all expectations, it resulted in a tetramethyl superiority of 1.2 to 1.9 engine octane units. which contains these constituents, namely o-, m- and * p-xylenes, and 0.837 g of lead per liter in the form of tetramethyl lead, is a preferred embodiment of the invention. The results achieved with trimethylbenzene are even more striking. Using this component, and 0.837 g / Iiter lead in the form of tetramethyl lead, an advantage of 2.8 Motor Octane Number units in Vergleioh to the equivalent amount of lead in 3? Orm of tetraethyl scored "Similar octane improvements provide other methyl-substituted benzenes, such as _e 1.2 , 3-trimethylbenzene, l, 3 | 5-trimethylbenzene and 1,2,3,4, 1,2,3,5 and _f l 2.4 »5- £ someren of tetramethyl benzene"

809801/0359 _ ₁₈ "

The above results clearly show that a higher octane improvements with the aromatics according to the invention genes can be achieved, and these are also greatest under the conditions of the Motor Method Test.

The following examples serve to illustrate exemplary embodiments of the invention.

Example I.

A propellant was made from 30 # catalytically cracked material, 10 $ alkylate, and 6O56 catalytically reformed material. The reformate contained 5 # toluene and other ingredients including benzene, ethylbenzene, diethylbenzene, propylbenzene, isopropylbenzene, butylbenzene and the like. The fuel had an initial boiling point of 36.7 ° O and a final boiling point of 196 ⁰ O. He was tetramethyl lead added in an amount corresponding to 0.132 g / liter. The fuel had the properties of the compositions according to the invention.

Example II

The fuel was composed of 10 $ light, direct distilled, 2056 catalytically cracked and 70 # catalytically reformed material. The reformate contained 20 $ 0-, m- and p-xylene mixtures. The fuel had an initial ^{boiling point of 35.0 0} O and an end boiling point of 207 ° 0. 0.837 g / Ll-over lead as tetramethyl lead was added to it. The fuel had its own high octane property ·; »! and works well for combating rapid tapping.

-19-809801 / 0359

142093?

Example III

This fuel consisted of 10 $ light, directly distilled material, 10 # polymeric material, 10 $ conductive, catalytically cracked material, 50 $ catalytically reformed material and 20 # a mixture of 1,2,3- »1,2 , 4-and 1,3,5-isomers of trimethylbenzenes. The reformate contained 17 # benzene, 10 $ toluene, 9 mixed xylenes, 14 # ethylbenzene, 14 $ mixed isomers of trimethylbenzene, 796 isopropylbenzene, 13 $ butylbenzene, 159% saturates and the remainder traces of various other aromatics. Its initial boiling point was 33 "3 ⁰ O and his final boiling point at 191 ° 0th 0.264 g / liter of lead in the form of tetramethyl lead was added to it. »The fuel is extremely suitable for combating rapid knocking.

Beis piel IV

A fuel was made up of $ 30 catalytically cracked material, $ 10 alkylate, and $ 60 catalytically reformed material. The reformate contained 5 $ toluene and also, for example, benzene, ethylbenzene, diethylbenzene, propylbenzene, isopropylbenzene, butylbenzene and the like. The fuel had an initial ^{boiling point of 36.7 0} O and an end boiling point of 196 ⁰ O. A mixture of 75 mol of tetraethyl lead and 25 mol of tetramethyl lead was added to it in such an amount that the liter contained 0.132 g.

BATH ORIGINAL

8 'J :: C U 1 / ü 3 5 5

Example Y

The fuel consisted of 10 "t" light ", directly distilled material, 20 # catalytically cracked material and 70" catalytically reformed material. The reformate contained 20 t of a mixture of o-, m- and p-xylene. The fuel had a Anfangesiedepunkt 35, O, and ⁰ O. a final boiling point of 207 ⁰ C. In liters of 0.837 g in the form of a Tetraalkylblelmlsohung zugemleoht containing methyl 753C and 253 * Äthylradikale and au "30 percent by weight tetramethyl lead, 42.1 Gewiohtsproeent Äthyltrimethylblei, 22.2 weight percent Diäthyldimethylblei, 5 | 2 weight percent Triäthylmethylblei and 0 _for 5 percent tetraethyl consisted · The fuel has its own high octane characteristics and is suitable for controlling Sohnellaufklopfen.

Example VI

This fuel was made from $ 10 light direct distilled material, $ 10 polymer, 10 # light catalytically cracked material, $ 50 catalytically reformed material, and $ 20 a mixture of the 1,2,3, 1,2,4 and 1 , 3 »5 isomers of trimethylbenzene ausammengesteilt. The reformate contained 179 * benzene, 10 $ toluene, 8 $ mixed xylenes, 14 $ ethylbenzene, 14 $ mixed isomers of trimethylbenzene, 7 # isopropylbenzene, 13 $ butylbenzene, 15 $ saturated materials and in the remainder traces of various other aromatics. In the case of this fuel, the initial ^{boiling point was 33.3 0} O and the end boiling point 191 ⁰ O. Per liter of fuel, 0.246 g of lead in the form of a mixture of

809Ö0 1/0359 BAD ORIGINAL _ ^ _

been set, tetraalkyllead anti-knock compound / "dTe 25 * contained methyl and 759 * Äthylradikale and - by weight - from 0.4 # TML, 4.3 # Äthyltrimethylblti, 20.2 # Di * thyldimethylblei, 42.1 * Triethylmethyl lead and 33, Ο? Έ tetraethyl lead

The fuel is excellent for fighting of rapid tapping

Example YII

The fuel consisted of 40 $ catalytically cracked material, X596 light, direct distilled material, 155 ^ alkylate, 27% polymer and 3 # trimethylbenzene. His Anfangesiedepunkt was 40.5 ⁰ O and his Bndsiedepunkt at 210 ° 0th A mixture of 25 mol # of tetraethyl lead and 75 mol of tetramethyl lead was added in such an amount that its concentration per liter was 0.396 g,

Example VIII

This fuel consisted of 20 # light, directly distilled material, 30 ^ catalytically cracked material, 15 $ a mixture of the 1,2,3,4-ι 1,2,3,5- and 1,2,4,5-isomers of tetramethylbenzene, reformate and alkylate. Be Anfangseiedepunkt was 33.3 ° E and its final boiling at 221 ⁰ C. A 50 # 50 # methyl and ethyl radicals containing mixture tetraalkyl-anti-knock agent - by weight - from 5.71 * tetramethyl lead, 23, and 37 Äthyltrimethylblei , 4 # diethyldimethyl lead, 26 # triethylmethyl lead and 6.9 # tetraethyl lead were added in such an amount that their concentration in the liter was 0.528 g

fraud.

8 0 9 8 0 1/0359 ^{BAD 0R} * GJNAL

The fuel is okay. good for combating sonar knocking »

Example II

This fuel consisted of 155 * directly distilled material, 4-55t catalytically cracked material, 5 # toluene, 7% o-xylene, 13% m-xylene, 10% p-xylene and 5% 1,2,4-trimethylbenzene. So much of a "physical" mixture of 50 mol- ^ tetratethyl lead and 50 mol-ft tetramethyl lead was added to it that 0.396 g of it was present per liter. His Anfaiigssiedepunkt was 31 "7 ⁰ G and his final boiling 199 ⁰ O.

Example X

This fuel mixture consisted of 10ft alkylate, 655 * toluene, 15 # lightweight directly distilled material and 10 $ polymer had an initial boiling point of 33f3 ° O and a final boiling point of 192 ⁰ C and contained per liter 1 | 585 g of lead in the form of an " physical mixture of 21 mols of tetramethyl lead, 21 mols of tetraethyl lead, 29 mols of methyltriethyl lead and 29 mols of tri-diethyl lead. This fuel had extremely high octane properties that are well suited for combating both slow and high-speed knocking.

Example XI

This fuel consisted of 35 # light, direct distilled material, 30 # catalytically cracked material,

-23-809801 / 0359

Ioluol, ldjfc a mixture of ο-, m- and p-xylene,

a mixture of the 1,2,3- »1 * 2,4- and 1,3> 5-isomers of trimethylbenzene and 10j a mixture of the 1,2,3» 4 ··, 1,2,3,5- and 1,2,4 »5 isomers of tetramethylbenzenes. Its initial boiling point was at 4 to 0.5 ⁰ O and its final boiling at 193 ⁰ O. Him wurdtn j · liter 0.792 g of lead in the form of a letraalkylbleimisohung added, the alkyl groups of from to 2556 Μ * 1φ3: 1 and passed to 75Ji from ethyl.

Although the invention consists in that the

Antibenes / knocking agents in the specified concentrations in the specific methyl-substituted benzenes containing If fuels are used, the methylbenzene need not be the only aromatic present. It can other aromatics may also be present, and such will in fact be used in many practical applications in view of added to the propellants according to the invention, based on the current refining technique. Even with solohen Compositions still see the benefits of using methyl substituted benzenes.

As the above examples show, the aromatic constituents can be incorporated into gasolines composed of all possible basic materials. These include materials that are distilled off directly, catalytically or thermally cracked materials, catalytic reformates, alkylates, isomerized Li materials and the like. In general, the finished gasolines according ASTIvi method I) 86 should have an initial boiling point of about 29.4 ° to 40.5 ⁰ O and a final boiling point of about 185 ° to 221 ⁰ O

BATH ORIGINAL

-24-8098Ü1 / U35 9

own. Because of their volatility erwünsohten are toluene, the xylene isomers, trimethylbenzene and tetramethylbenzene well suitable additives for conventional gasolines "The boiling point of these aromatic compounds is in the range zwisohen about 82 ° and 210 ⁰ O and thus well within the range of commercial gasolines.

The aromatics used in the fuels according to the invention can come from various sources · They can be obtained by refining and processing petroleum, come from coal processing or can be synthesized from a wide variety of starting materials by any known process · Manufacturing process for the lead alkyd starting materials and the "chemical" Mixtures are known and published in the literature. If desired, other octane-improving additives can be used in addition to the alkyl lead anti-knock agents. These include other organic lead compounds such as tetrapropyl lead, tetraphenyl lead, transition metal compounds such as methylcyclopentadienylinangane tricarbonyl, cyclopentadienyl manganese tricarbonyl, cyclopentadienylnickel nitrosyl, manganese perita carbonyl, iron carbonyl, dioyclopentadienyl iron and dioyclopentadienyl iron. Other anti-knock improvers, which also to ^ eset:; iv / earth] ;. öjtinen,. are Gfn'lioiJijäureester as Tcrtiärbutylaotitat, amine salts oi'f'auiiiS'.Ler acids such Iroijut>"laininisobutyrat, Athylajiiin- ^ fc (jl · -ni n.Rthylprofi onnt, n-lropylaiuinpropionrit uu <\ ^ üer leiclien. Ditre OktanverLeirGra'er iiounejj zuiir the ERJ indun ^ Bfeufasaeii Tr <i ■■ :. κ ilen Kugetei; - be their Vei "vi dun ^ but to au suddenly and kcinetfalla required.

8 Π Π f>ι; 1 / ίΐ ^ Γ UUoL I / υ ό b a

In the case of the improved propellants according to the invention can also be used with organohalogen optics, those made from either aliphatic or aromatic hydrocarbons or mixtures of both may exist, in which halogen is attached to the carbon of the aliphatic or aromatic part of the molecule is bound. They can also be made from carbon, hydrogen and oxygen-containing compounds. bonds such as haloalkyl ethers, hydrogen halide halonitro compounds and the like. Mixtures of different detergents can also be used. Concentrations of the organohalogen detergent range from about 0.2 to about 2.5 theoretical units - on lead calculated - are sufficient, but larger or smaller quantities can also be used. A theoretical detergent unit means the amount that is theoretically required to remove all of the lead during combustion to convert in the I; otor into volatile lead halides and thereby the extent of the deposits that form in the engine to control effectively. Examples ■ of this are!

a gasoline with $ 15 toluene, 0.396 g / liter lead in Form of tetramethyl lead or as a "physical" mixture of 50 mol- $ tetraethyl lead and tetramethyl lead, 0.5 theoretical bromine units in the form of ethylene dibromide and 1.0 theoretical Chlorine units in the form of ethylene dichloride

a gasoline with $ 20 of a mixture of xylene isomers and 0.660 g / liter of lead in the form of tetramethyl lead or a tetraalkyl lead anti-knock mixture $ 75 methyl and $ 25 ethyl radicals. This mixture was by weight of 30.0 $ tetramethyl lead, 42.1 $ ethyltrimethyl lead, 22.2 $ diethyldimethyl lead, $ 5.2 triethylmethyl lead and $ 0.5

8098U 1/0359

as well as a theoretical bromine unit in 7orn composed of ethylene dibromide)

a gasoline with 259 * T e tr ame thy Ib enz oil, 0.792 g / liter Lead in the form of tetramethyl lead or a Tetraalkyl lead anti-knock mixture with 253 * methyl and 7556 ethyl radicals (consisting of - on Weight basis -0.4% tetramethyl lead, 4.3% Ethyl trimethyl lead, 20.2% diethyldimethyl lead, 42.1% triethylmethyl lead and 33.0% tetraethyl lead) and 0.5 theoretical bromine units in the form of mixed Dibromotoluolej

a gasoline with $ 15 tetramethylbenzene, 1.057 g / liter Lead in the form of tetramethyl lead or a tetraalkyl lead anti-knock mixture with 50% methyl and 5096 ethyl radicals (consisting of - on Weight B basis - 5.7% tetramethyl lead, 23 »8% Ethyl trimethyl lead, 37.4? Ί diethyl dimethyl lead, 26.2% triethylmethyl lead and 6.9% tetraethyl lead) and 2.5 theoretical ortho units in the form of 1,2,4-trichlorobenzene

and similar types of gasoline.

The propellants according to the invention can also contain other additives. These include, for example, antioxidants, such as N, N ¹ -di-secondary butyl-p-phenylenediamine, pN-butylaminophenol, 4-methyl-2,6-di-tertiary butylphenol, 2,6-di-tertiary butylphenol, etc., metal clocklvators such as NjN Disalioylidene-l ^ -diaminopropane, etc., dyes, phosphorus additives, such as tri ($ - chloropropyl) thionophosphate dimethyltolyl phosphate, dimethyl alkyl phosphate, phenyl dimethyl phosphate, trioresyl phosphate, phenyldicresyl phosphate, phenyldicresyl phosphate, phenyldicresylphosphate, phenyldicresylphosphate, trimethylphosphole, beethylphosphole, trimethylphosphole, beetethylphosphate, beetethylphosphate, beetethylphosphole, beetylphosphole, dehydrated phosphate, salicophosphole, oreylphosphate, salaphospholyl) thionophosphate, tri ($ - chloropropyl) thionophosphate, , Anti-corrosion agents, cleaning agents and the like. 809001/0359 ^B * D ORIGINAL

Claims (2)

142093B 1. Leaded gasoline composition, characterized in that that they have about 3 to 65 # !! ethylbenzene with 1 to 4 methyl groups and 0.132 to 1.585 g / liter of lead as an anti-knock agent in the form of tetraalkyl lead containing alkyl groups consist of at least $ 25 of methyl groups. 2. Composition according to claim 1, characterized in that it contains 0.132 to 1.585 g / Lli; er lead as an anti-knock agent in the form of tetramethyl lead present alone. 3. Composition according to claim 1, characterized in that it contains 0.132 to 1.585 g / liter of lead as an anti-knock agent in the form of tetramethyl lead which is mixed with other alkyl lead compounds in an amount of at least about 25 percent by weight is present. 4 «Composition according to any one of claims 1 to 3, characterized characterized in that it contains a physical formulation of alkyl lead compounds, both ethyl and Contains ethyl radicals. 5 · To :: ar.: I; ieii, set: u; ü] £ according to one of the Ai] proverbs 1 to 3, whereby f _ (. Lu) ui zt rejects the fact that the alkylb] eiveruindungsmixture üurcii Ki: <ii 1 ■ ^ j rearrangement between tetraruethyl leadi uud Tti.2 ¹ JiUIt Ji: (: d '. ÜtBtanden j & t, ujo In Ge _L ; eiAva2 * t tlve. Jilui-.i) jiiiiiji.-ij r.ii _: eijicij · -.italysuiorti ^ '- """- i-ciit v.'uruon. c _e ... u: ·: j lüftji. it: u;: iK iLui ii cij.oifi out jh; · / rüciie 1 bie | 5, düaurch ._ci: r ι: ά. .!. i. "j < _: ", aass ί »1 ( ^Λ l; .i c-, ü.: üj ie ι, ί ',' ί: .l:. ι :,;," / .j , Liters punished, BATH ORIGINAL 7. Composition according to claim 6, characterized in that it contains 0.660 to 0.925 g / L ± -ter lead in the form of tetramethyl lead. 8 «Composition according to any one of claims 1 to 7» daduroh marked that they are about 5 to 20 # in the form of a Mixture of dimethylbenzene isomers or trimethylbenzene contains. 9 · Composition according to one of claims 1 to 7 »daduroh characterized in that it is 5 to 15ji 1,2,4-trimethylbenzene contains. BATH