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Патент USA US3074798

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United States Patent 0 ’ 1C6
3,074,788
Patented Jan. 22, 1963
2
1
combustion chamber. The minimum amount of 0.1% of
1,1,2,2-tetrachloro-1,2-di?uoroethane, based on the weight
3,074,788
of the gasoline, corresponds to 2.6 theories of total halo
gen based on 3 ml. of tetraethyllead per gallon of fuel.
Blaker employed a 100‘ hour test in a single cylinder Lau
son engine and reported that the induction system and
ANTIKNOCK COMPOSITIONS
Edmund L. Niedzielski, Graylyn Crest, Wilmington, DeL,
assignor to E. I. du Pont de Nemours and Company,
Wilmington, DeL, a corporation of Delaware
No Drawing. Filed Apr. 5, 1960, Ser. No. 19,992
16 Claims. (Cl. 44—69)
valves were clean with no evidence of valve burning.
However, it has now been found that, when such amounts
of l,l,2,2-tetracliloro-l,Z-difluoroethane are used in fuel
This invention relates to antiknock compositions and
employed in multiple cylinder engines, particularly over
more particularly to compositions of organolead anti 10 longer periods of time, objectionable burning on at least
knock compounds and novel combinations of halohydro
some of the valves frequently occurs, as shown particular
carbon scavenging agents for the lead.
ly by changes in compression pressure. Usually, visual
‘organolead antiknock compositions are widely used to
inspection alone cannot adequately detect valve burning
improve octane ratings of fuels for high compression Otto
even after exposure times of 200-300 hours, but changes in
cycle engines. These compositions consist essentially of
15
the organolead antiknock agent and at least one halo
hydrocarbon that is a scavenger for lead in the combustion
process,‘that is, is able eventually to convert the lead con
tent of the organolead into relatively volatile lead halides.
compression pressure can be relied upon to give indica
tions of valve burning under proper test conditions.
It is an object of this invention to provide novel organo
lead antiknock blends. Another object is to provide or
ganolead antiknock blends containing a mixture of halo
In the absence of halohydrocarbon scavenger, build up of 20 hydrocarbon scavenging agents which materially decrease
lead-containing deposits soon becomes excessive for
the burning of exhaust valves and other di?iculties that
smooth functioning of the engines. Even with e?icient
tend to arise in the use of organolead antiknock compo
undergoing combus
. scavengers present in the fuel charge
tion, deposits gradually accumulate. Such accumulation
is particularly troublesome in high compression engines
25
such as those of present day passenger cars and trucks,
especially under the conditions of low speed and light load
sitions containing halohydrocarbon scavenging agents in
fuels for Otto cycle engines. A particular object is to
provide tetrahydrocarbonlead antiknock blends containing
1,1,2,2-tetrachloro-l,Z-difluoroethane and other halohy
drocarbon scavenging agents which overcome the disad
vantages and dif?culties heretofore encountered in the use
cause or lead to (1) increased octane requirement of the
of 1,1,2,2-tetrachloro-1,2-di?uoroethane as a scavenging
30
engine, (2) premature ignition of the fuel charge, (3)
agent. A further object is to provide antiknock compo
spark plug fouling, and (4) malfunctioning as well as de
sitions of the aforesaid character which, as additives in
creased life of the exhaust valves.
hydrocarbon fuels for Otto cycle engines, are effective to
This invention is directed primarily to alleviating the
improve exhaust valve performance as well as to control
difficulties associated with malfunctions resulting from the
the accumulation and character of combustion chamber
35
accumulation of deposits on and corrosion (burning)
deposits. Another object is to provide new fuel compo
of the exhaust valves. For example, high spots (accumu
sitions comprised essentially of hydrocarbon fuels for Otto
lated deposits) and low spots (actual loss of metal by cor
cycle engines and the aforesaid antiknock compositions.
rosion) on the face and seat of an exhaust valve prevent
Still other objects are to provide new compositions of mat
proper positioning (closing) of the valve. The result is 40 ter and to advance the art.
valve leakage, indicated by undue variations in compres
The above and other objects may be accomplished in
sion pressures, and consequentially poor engine perform
accord with this invention which includes tetrahydrocar
ance. Valve burning is the more severe condition, de
bonlead antiknock blends comprised essentially of a tetra
pendent more on the corrosive nature of the exhaust gases
hydrocarbonlead antiknock compound and a mixture of
and deposits than on the amount of the deposits. The 45 halohydrocarbon scavenging agents providing 0.1 to about
corrosivity of these substances appears in some way re
0.33 theory of ?uorine, 0.3 to about 0.5 theory of bromine,
lated to the composition of the antiknock additive con
and suf?cient chlorine to make a total of 1 to about 2
ventionally de?ned in terms of the theories of halogen as
theories of halogen, said mixture of halohydrocarbon
exempli?ed by “city driving.” The deposits ultimately
halohydrocarbon per atom of lead as organolead, one
theory of halogen being that quantity of halohydrocarbon
stoichiometrically required to convert all the lead of the
scavenging agents consisting of 1,l,2,2,-tetrachloro-l,2
50 difluoroethane in an amount to provide all of said ?uorine
organolead to lead dihalide. However, present knowledge
provides insufficient basis for predicting the effects of dif
and at least part of said chlorine and at least one halo
hydrocarbon in which each halogen has an atomic weight
between 35 and 80 in an amount to provide all of said
ferent lead scavenging compositions on exhaust valve per
bromine and the rest of said chlorine; and fuels for Otto
55 cycle engines comprised essentially of hydrocarbon fuels
formance.
R. H. Blaker in US. Patent 2,784,160 discloses that
in the gasoline boiling range containing said antilcnock
certain ?uorine-containing halohydrocarbons, including
compositions in an amount to provide 0.5 to 4 ml. of the
tetrahydrocarbonlead antiknock compound per gallon of
1,1,2,2,-tetrachloro-1,Z-di?uoroethane, are effective to
overcome some of the adverse effects of deposits in Otto '
fuel.
cycle engine operations, when present in the combustion 60 It has been found that the tetrahydrocarbonlead anti
knock blends of this invention, when so used in fuels for
chamber in amounts corresponding to from about 0.1%
Otto cycle engines, lead to signi?cant improvements in
to about 2% by weight of the hydrocarbon fuel. They
decrease the equilibrium octane requirement of the engine
and also usually decrease the amounts of deposits in the "
exhaust valve performance while efficiently scavenging
lead during the operation of the engine, decreasing the
a, vegan
P.)
will
equilibrium octane requirement of the engine, and de
creasing the amount and altering the character of deposits
in the combustion chamber.
chloroethane. However, other halohydrocarbons of the
broad class may be employed, such as mixed dibrorno
When the antiknock com—
toluenes, dichlorotoluenes, brornochlorotoluenes, propyl
positions of this invention are employed in the hydro
ene trichloride, propylene tribromide, and like bromohy
carbon fuels in an amount to provide 4 ml. of tetrahydro
carbonlead per gallon of fuel, the concentration of the
drocarbons, chloro-hydrocarbons and bromochlorohydro
carbons. Preferably, a mixture of ethylene dibromide and
l,1,2,2-tetrachloro-LZ-diiluoroethane will be employed to
l,1,2,2-tetrachloro-l,Z-di?uoroethane based on the total
fuel composition will be less than 0.055% by weight.
provide the required theories of ?uorine, bromine and
The improved Valve performance shows up during ex
chlorine.
tensive engine operation as less valve leakage, narrower 1O
As is conventional in this art, the tetrahydrocarbonlead
?uctuations in compression pressure from one cylinder
antiknock blends of this invention usually will contain a
to another of multicylinder engines, and less valve burn~
small proportion of an identifying dye and a minor pro
ing. The overall effects are smoother multicylinder op
portion of an inert solvent oil, usually kerosene, and may
eration and longer valve life. The high scavenging ef
also contain stabilizers, metal deactivators, and the like.
ficiency provided by the combination of halohydrocarbon 15
The combination of tetrahydrocarbonlead and mixture
scavenging agents of this invention is indicated by less
of haiohydrocarbon scavenging agents of this invention
ened tendencies of an engine to show increase in its oc
will be employed in the conventional fuels for Otto cycle
tane number requirement on prolonged operation. On
engines which essentially are hydrocarbon fuels in the
the other hand, the novel compositions of this invention
gasoline boiling range, including cracked gasolines and
do not exert a signi?cant deleterious effect on the per 20 synthetic fuels composed of a single hydrocarbon or a
formance of the fuel or on other aspects of engine oper
mixture of hydrocarbons in said boiling range. Such
ation.
fuels may also contain identifying dyes, antioxidants,
The tetrahydrocarbonlead antiknock compounds may
metal deactivators, anti-icing agents and other functional
additives normally associated with ?nished commercial
be any of those which are known to the art as antiknock
agents for hydrocarbon fuels for Otto cycle engines. 25 motor fuels.
The hydrocarbon radicals in the tetrahydrocarbon lead
Such motor fuels will-contain the tetrahydrocarbon
may be alkyl or aryl, such as methyl, ethyl, propyl, butyl
lead antiknock compound in a proportion of from 0.5 to
and phenyl. Usually, the antiknock compound will be a
4 ml. per gallon of fuel and the corresponding propor
lower tetraalkyllead in which the akyl groups are methyl
tions of the halohydrocarbon scavenging agents. When
or ethyl, such as tetraethyllead, tetramethyllead, dimedlyl
so used, the concentration of the l,l,2,2-tetrachloro-l,2
diethyllead, methyltriethyllead, trimethylethyllead, and
dilluoroethane will be less than 0.055% by weight based
mixtures of any two or more thereof. Preferably, the an
on the total fuel composition. Usually, it will be desired
to employ the l,1,2,2-tetrachloro-1,2-difluoroethane in a
concentration of ‘at least 0.01% by weight of the fuel
composition. Absolute concentrations of the 1,1,2,2~
tiknock agent will be tetraethyllead, which is readily avail
able commercially, or a mixture thereof with tetramethyl
lead.
The 1,1,2,2-tetrachloro-1,Z-di?uoroethane may be used
in a proportion to provide as little as 0.1 theory of flu
tetrachloro-l,2-di?u0roethane materially greater than
0.055% by weight of the fuel composition tend to pro
mote valve burning. Further improvements are obtained
orine and 0.2 theory of chlorine and as much as about
0.33 theory of fluorine and about 0.67 theory of chlorine.
Preferably, it will be employed in a proportion to pro
vide at least 0.2 theory of ?uorine and 0.4 theory of chlo
rine and, most preferably, to provide about 0.33 theory
of ?uorine and about 0.67 theory of chlorine. The term
“theory” of halogen is a conventional term commonly
40
ethane and the other halohydrocarbon scavenging agents)
an organophosphorus compound to minimize preignition
tendencies of the engine and to reduced spark plug fouling,
such organophosphorus compounds being well known in
employed in this art to de?ne the amount of halogen as
halohydrocarbon per atom of lead present in the tetra
the art.
The ?uoro-chloro-ethane may be employed as a blend
hydrocarbonlead antiknock compound, one theory of
with the other ingredients or it may be added separately
halogen being that quantity which is stoichiometrically
required 0t convert all of the lead of the tetrahydrocar
bonlead to lead dihalide, i.e. 2 atoms of halogen for
each atom of lead in the composition.
In addition to the 1,1,2,2-tetrachloro-1,2-di?uoroethane,
it is essential that the antiknock composition or the fuel
contain at least 0.3 theory of bromine in the form of a
halohydrocarbon in which each halogen has an atomic
Weight between 35 and 80. Omission of the bromine en
tirely or reducing it materially below 0.3 theory, tends
to result in the opposite and harmful eifect of valve leak
age due to valve burning. Usually and preferably, the
compositions of this invention will contain such halo
hydrocarbon in an amount to provide about 0.5 theory
of bromine.
The compositions of this invention should contain a
total of 1 to about 2 theories of halogen, ?uorine plus
bromine plus chlorine. When the amounts of 1,l,2,2
tetrachloro-l,2-di?uoroethane and bromohydrocarbon are
insufficient to provide the desired amount of halogen, a
by employing (along with the tetrahydrocarbonlead anti
knock compound, the 1,1,2,2-tetrachloro-l,Z-difluoro
or in combination with any one or more of the other in
gredients, ‘as described by Blaker in U.S. Patent 2,784,160;
50 provided of course it is present in the combustion chamber
in the proportions and amounts given above ‘at the time
the fuel charge is ignited. Preferably, it will be employed
along with the other ingredients as a blend, e.g. as a tetra
55
ethyllead antiknock composition.
Some typical antiknock compositions are illustrated
below, wherein TEL stands for tetraethyllead. The
quantities are in parts by weight.
60
The compositions are
prepared by mixing the ingredients (in any order) to pro
duce homogeneous blends.
Examples: Antz'knock Compositions
Parts I
65
Theories Halogen
Example 1:
chlorine-containing halohydrocarbon should be included
TEL ________ __
4. 95
to provide the additional amount of halogen required.
FG1200012F__
Bl‘CHgCHBBl'-
1. 04 1.0 (0.67 C1+0.33 F)
The halohydrocarbon scavenging agents in which each
halogen has an atomic weight between 35 and 80, i.e. 70
is bromine or chlorine, are well known to those skilled in
the art.
Preferably, such halohydrocarbon scavenging
agents will be the conventional ethylene dihalides such as
ethylene dibromide, ethylene dichloride, and 1-brorno-2~ 75
1. 44
.5 Br
3,074,785;
.5
6
etc, and, as a result, show greater or lesser tendencies
to accumulate deposits in the valve area and to suffer
Examples: Antiknock Compositions-Continued
corrosive attack with consequent pressure leakage.
In the tests described below, a late model 10:1 com
4.95
0.78 0.75 (0.50 C1+0.25 F)
pression ratio V-8 engine was operated on a given fuel
1. 44 0. 5 Br
200 hours under the following cyclic conditions: 3.3
minutes at 2000 rpm. and 25 brake horse power, de
celeration under load to idle, ‘1 minute idle at 700 r.p.m.
0. 76 0. 5 Cl
7. 93 1. 75
Example 4:
'
TE
__________________________ ._
11011000121?“
and acceleration under load with one of 4 accelerations at
4. 95
0.31 0.3 (0.2 Cl+0.1 F)
BI‘CHzCHzBL
1. 44 O. 5 B!‘
ClCHzCHgCl _________________ __
1. 52
10 wide open throttle and 3 at part throttle. The base fuel
in each test was the same blended gasoline, an article of
commerce, to which was added an antiknock composition
1.0 01
8.22 1.8
consisting of tetraethyllead (TEL) in quantity su?icient
to give a concentration of ‘3 m1. of tetraethyllead per gal
The lubri
Example 5:
TEL __________________________ __
FClgOCChF“
4. 95
1.04 1.0 (0.67 Ol+0.33 F)
BI‘CHqOHgBI‘ __________ __
1. 44
Tolyl diphenyl phosphate-
0. 69 0. 2 P 1
15 lon and other ingredients as speci?ed below.
cant was a standard crankcase lubricating oil composition
which, like the base fuel, was not critical for the invention.
The effects of antiknock compositions on exhaust valves
O. 5 Br
8.12 1. 7
(performance and condition) were determined by (a)
Example 6:
TEL; ________________________ _.
4. 95
FClzCCCl2F____
0.31 0.3 (0.2 Cl+0.1 F)
CIOHQOHIC'I _________________ _.
0. 61
BrCHgCH1Br___
20 visual inspection of the valves (seats and faces) for de
posits, signs of burning, and degree of seating, and (b)
0. 87 0.3 Br
measurements of the compression pressure of each cylin
der before and after the engine test.
0. 4
6.74 1. 0
The compression pressure of a cylinder was the maxi
1 The total weight of the composition when added in grams to each 25
gallon of a gasoline rovides 3 ml. or TEL (tetreethyllead) per gallon.
It should be noted a so that 1.04 grams of FClzCCClrF per gallon of gas
mum pressure attained, using the CPR compression‘ gage,
by cranking the engine over a minimum of :10 revolutions.
All measurements were related to a ?xed cranking speed
oline corresponds to about 0.04% by weight.
2 Theories of P are based on the stoichiometry of converting Pb of
of 180 r.p.rn., the correction being a change in p.s.i. of
TEL to Pb: (P04);
1 for a change in r.p.m. of 5.
30
‘Valve Performance: Methods and Examples
'
The examples below show that the range in A compres
sion' pressure and the extent of exhaust valve leakage is
minimal when the engine is operated on a fuel composi
tion according to the invention.
During the operation of an engine, the compression
Changes in Cylinder Compression Pressure and Octane
Requirement
Cyclic Engine Test: 200 hours
Engine: V-8, 10:1 Compression Ratio
Fuel: Gasoline + 3 m1. TEL/gal. + Scavenger
.
Test
A Compression Pressure at 180 r.p.m., p.s.i. in
Scavenger, Theories 1
Cylinder N0.—
Equil.
Octane
Require
ment
1
Non __________________________________ __
2
3
4
5
6
7
8
Range
4
16
13
17
19
ll
11
14
15
.
10
7
—41
10
—45
4
11
27
6
13
7
13
9
12
3
16 —2
2 15
18
0
15
3
1
18
98. 3
72 ________ _.
59
98. 8
_ 0.5 Br+1.0 FClzCCClzF _______ __
0.5 Br+1.0 FChOOClzF-l-O? P ________ __
12
22
11
23
9
19
14
18
11
21
10
19
14
22
_ 0.5 Br+1.0 Cl _____________ _.
_ 0.5 Br+1.0 Cl-l-2.6 FClzCCClzF_
_ 1.5 FClzOCC F ........... __~__._
14
19
5
5
________ __
97. 0
________ __
1 Br as ethylene dibromine; 01 as ethylene dichloride; P as tolyl diphenyl phosphate; 1.0 FClzCCClrF is
equal to 0.67 Cl+0.33 F.
Tests 5 and ‘6 illustrate use of novel compositions of
pressure gradually increases ‘as a result of deposit build 50
this invention. Tests 1~4 are for comparison only.
up within the combustion chamber. The increase for
‘Test'2 shows the typical behavior of exhaust valves
each cylinder can be measured and, as in the examples
when the conventional tetraethyllead automotive mix is
below, expressed as A compression pressure in p.s.i. In
.present in the gasoline.
' general, cylinders showing the smallest (even negative)
increases in compression pressure are those suffering pres 55 ' In test 3, 2.6 theories of FCl2CCCl2F is equivalent to
0.1% by weight of the gasoline; this test was stopped after
sure loss. Valves, which visibly seat poorly due to deposits
137 hours. The exhaust valve of the No. 2 cylinder was
or burning, invariably belong to the cylinders that show
the smallest positive change in pressure.‘ I It should be
severely burned, as indicated by the ——45_ p.s.i. change
pears inherent in the design of the engine, for example,
in the design pattern of the fuel intake and distribution
Test No. 4 likewise shows valve burning (No. 1 valve)
and relatively poor performance of valves Nos. 2, 5, 7 and
understood that not all valves need be fouled or burned ' ‘ in compression
to the same extent. Why one burns and another not ap 60 nation.
pressure and con?rmed on visual exami
system. It is well known that, in a V~8 engine for ex
The relatively small change in compression pressures
ample, the distribution of they fuel charge may vary from '
'one bank to the other, and from one cylinder to another 65 in tests 5 and 6 illustrates the smooth valve performance
in‘ the presence of the compositions of this invention;
there is no signi?cant tendency to valve leakage and burn
ing, con?rmed on visual examination of each valve’s face
‘and seat for deposits and corrosion. Further, test 5
some cylinders may on the average be running on richer 70 shows a signi?cant -1.3 octane number reduction‘ in the
requirement of the engine over the conventional anti
orleaner charges than others or may be receiving some
knock mix of test 2.
what different proportions of the scavenging composition,
in each bank. The composition of the fuel charge, with
regard to fuel/air ratio, antiknock concentration, scav
enger concentration, and light and heavy fuel ends, tends
to vary from one part of the engine to another. Thus,
3,074,788
7
It will be understood that the preceding examples have
been given for illustrative purposes solely and that, sub
ject to the limitations set forth in the general description,
many variations can be made in the compounds and pro
portions thereof employed without departing from the
spirit or scope of this invention.
From the preceding, it will be apparent that this in
to provide about 0.5 theory of bromine and l,1,2,2-tetra
chloro-l,Z-di?uoroethane in an amount to provide about
0.33 theory of ?uorine and about 0.67 theory of chlorine.
7. A tetraethyllead antiknock blend consisting essen
tially of tetraethyllead, ethylene dibromide in an amount
to provide about 0.5 theory of bromine and l,l,2,2-tetra
chlOrQ-LZ-di?uoroethane in an amount to provide about
vention provides novel tetrahydrocarbonlead antiknook
0.2 theory of ?uorine and about 0.4 theory of chlorine.
8. A tetraethyllead antiknock blend consisting essen~
provide new and unobvious results and effectively solve 10 tially of tetraethyllead and a mixture of halohydrocarbon
serious problems presented by related compositions and
scavenging agents providing a total of 1 to about 2 theo
their use. Particularly, it greatly decreases the deleterious
ries of halogen, said mixture of halohydrocarbon scaveng
e?ects of tetrahydrocarbonlead antiknock compositions
ing agents consisting of ethylene dibromide in an amount
and the scavengers commonly employed therewith on the
to provide 0.3 to about 0.5 theory of bromine, ethylene
valves of Otto cycle engines. Therefore, it will be ap
dichloride in an amount to provide about 0.4 to about
parent that this invention constitutes a valuable advance
1.0 theory of chlorine, and 1,1,2,2-tetrachloro-1,2-di
blends and fuel compositions for Otto cycle engines which
in and contribution to the art.
?uoroethane in an amount to provide 0.1 to about 0.33
The embodiments of the invention in which an exclusive
property or privilege is claimed are de?ned as follows:
theory of ?uorine and about 0.2 to about'0.67 theory of
chlorine.
9. A fuel for Otto cycle engines which consists essen
tially a hydrocarbon fuel in the gasoline boiling range,
1. A tetrahyd-rocarbonlead antiknock blend consisting
essentially of a tetrahydrocarbonlead antiknock compound
and a mixture of halohydrocarbon scavenging agents pro
viding ‘0.1 to about 0.33 theory of ?uorine, 0.3 to about
0.5 theory of bromine, and sui?cient chlorine to make a
total of 1 to about 2 theories of halogen, said mixture of
halohydrocarbon scavenging agents consisting of 1,?l,2,2
0.5 to 4 ml. of a tetrahydrocarbonlead antiknock com
pound per gallon of fuel and a mixture of halohydrocar
bon scavenging agents providing 0.1 to about 0.33 theory
of ?uorine, 0.3 to about 0.5 theory of bromine, and suf
?cient chlorine to make a total of 1 to about 2 theories
of halogen, said mixture of halohydrocarbon scavenging
tetrachloro-1,2-di?uoroethane in an amount to provide all
of said ?uorine and at least part of said chlorine and at
agents consisting of l,l,2,2-tetrachloro-1,Z-di?uoroethane
least one halohydrocarbon in which each halogen has an
in an amount to provide all of said ?uorine and at least
atomic weight between 35 and 80 in an amount to pro 30 part of said chlorine and at least one halohydrocarbon
vide all of said bromine and the rest of said chlorine.
in which each halogen has an atomic weight between 35
2. A tetrahydrocarbonlead antiknock blend consisting
and 80 in an amount to provide all of said bromine and
essentially of a tetrahydrocarbonlead antiknock compound
the rest of said chlorine.
and a mixture of halohydrocarbon scavenging agents pro
10. A fuel for Otto cycle engines which consists essen
viding about 0.2 to about 0.33 theory of ?uorine, about 35 tially a hydrocarbon fuel in the gasoline boiling range,
0.5 theory of bromine, and su?icient chlorine to make a
0.5 to 4 ml. of a lower tetraalkyllead antiknock compound
total of 1 to about 2 theories of halogen, said mixture of
per gallon of fuel and a mixture of halohydrocarbon
halohydrocarbon scavenging agents consisting of l,1,2,2—
scavenging agents providing about 0.2 to about 0.33 theory
tetrachloro-1,2-di?uoroethane in an amount to provide
of ?uorine, about 0.5 theory of bromine, and su?icient
all of said ?uorine and at least part of said chlorine and 40 chlorine to make a total of 1 to about 2 theories of halo
at least one ethylene dihalide in which each halogen has
gen, said mixture of halohydrocarbon scavenging agents
an atomic weight between 35 and 80 in an amount to
consisting of 1,1,2,2Ptetrachloro-1,2-di?uoroethane in an
provide all of said bromine and the rest of said chlorine.
amount to provide all of said ?uorine and at least part of
3. A tetraethyllead antiknock blend consisting essen
said chlorine and at least one ethylene dihalide in which
tially of tetraethyllead and a mixture of halohydrocarbon
each halogen has an atomic weight between 35 and 80
scavenging agents providing 0.1 to about 0.33 theory of 45 in an amount to provide all of said bromine and the rest
of said chlorine.
?uorine, 0.3 to about 0.5 theory of bromine, and su?‘i
cient chlorine to make a total of 1 to about 2 theories of
11. A fuel for Otto cycle engines which consists essen
halogen, said mixture of halohydrocarbon scavenging
agents consisting of l,1,2,2-tetrachloro-1,2-di?uoroethane
tially a hydrocarbon fuel in the gasoline boiling range,
in an amount to provide all of said ?uorine and at least
part of said chlorine and at least one halohydrocarbon
in ‘which each halogen has an atomic weight between 35
:and 80 in an amount to provide all of said bromine and
the rest of said chlorine.
mixture of halohydrocarbon scavenging agents providing
hydrocarbon scavenging agents consisting of 1,1,2,2-tetra
chlorine to make a total of 1 to about 2 theories of halo
all of said bromine and the rest of said chlorine.
amount to provide all of said ?uorine and at least part of
said chlorine and at least one ethylene dihalide in which
each halogen has an atomic weight between 35 and 80 in
an amount to provide all of said bromine and the rest of
mixture of halohydrocarbon scavenging agents providing
0.5 to 4 ml. of tetraethyllead per gallon of fuel and a
0.1 to about 0.33 theory of ?uorine, 0.3 to about 0.5
theory of bromine, and sufficient chlorine to make a total
of l to about 2 theories of halogen, said mixture of halo
4. A tetraethyllead antiknock blend consisting essen 55 chloro-1,2-di?uoroethane in an amount to provide all of
tially of tetraethyllead and a mixture of halohydrocarbon
said ?uorine and at least part of said chlorine and at least
scavenging agents providing about 0.2 to about 0.33 theory
one halohydrocarbon in which each halogen has an
atomic weight between 35 and 80 in an amount to provide
of ?uorine, about 0.5 theory of bromine, and sufficient
.
gen, said mixture of halohydrocarbon scavenging agents 60
12. A fuel for Otto cycle engines which consists es
sentially a hydrocarbon fuel in the gasoline boiling range,
consisting of 1,1,2,2-tetrachloro-1,2-di?uoroethane in an
said chlorine.
5. A tetraethyllead antiknock blend consisting essen
tially of tetraethyllead ethylene dibromide in an amount
to provide about 0.5 theory of bromine and 1,l,2,2-tetra
chloro-l,2-di?uoroethane in an amount to provide about
0.2 to about 0.33 theory of ?uorine and about 0.4 to
about 0.67 theory of chlorine.
6. A tetraethyllead antiknock blend consisting essen
tially of tetraethyllead, ethylene dibromide in an amount
0.5 to 4 ml. of tetraethyllead per gallon of fuel and a
about 0.2 to about 0.33 theory of ?uorine, about 0.5
theory of bromine, and sui?cient chlorine to make a total
of 1 to about 2 theories of halogen, said mixture of
halohydrocarbon scavenging agents consisting of 1,l,2,2
tetrachloro-1,2-di?uoroethane in an amount to provide ‘all
of said ?uorine and at least part of said chlorine and
at least one ethylene dihalide in which each halogen has
an atomic weight between 35 and 80 in an amount to
provide all of said bromine and the rest of said chlorine.
13. A fuel for Otto cycle engines which consists e's
sentially a hydrocarbon fuel in the gasoline boiling range,
3,074,788
about 3 to 4 ml. of tetraethyllead per gallon of fuel,
ethylene dibromide in an amount to provide about 0.5
theory of bromine and 1,1,2,2-tetrachloro-1,Z-di?uoro
10
sentially a hydrocarbon fuel in the gasoline boiling range,
about 3 to 4 ml. of tetraethyllead per gallon of fuel and
a mixture of halohydrocarbon scavenging agents pro
viding a total of 1 to about 2 theories of halogen, said
ethane in an amount to provide about 0.2 to about 0.33
mixture of halohydrocarbon scavenging agents consist
theory of ?uorine and about 0.4 to about 0:67 theory of
ing of ethylene dibromide in an amount .to provide about
chlorine.
0.5 theory of bromine, ethylene dichloride in an amount
14. A fuel for Otto cycle engines which consists es
to provide about 0.4 to about 1.0 theory of chlorine,
sentially a hydrocarbon fuel in the gasoline boiling range,
and l,1,2,2-tetrachloro-1,Z-di?uoroethane in an amount
about 3 to 4 ml. of tetraethyllead per gallon of fuel,
ethylene dibromide in an amount to provide about 0.5 10 to provide about 0.1 to about 0.33 theory of ?uorine
and about 0.2 to about 0.67 theory of chlorine.
theory of bromine and 1,1,2,2-tetrachloro-1,2-di?uoro
ethane in an amount to provide about 0.33 theory of
?uorine and about 0.67 theory of chlorine.
15. A fuel for Otto cycle engines which consists es—
sentially a hydrocarbon fuel in the gasoline boiling range, 15
about 3 to 4 ml. of tetraethyllead per gallon of fuel,
ethylene dibromide in an amount to provide about 0.5
theory of bromine and l,1,2,2-tetrachloro-1,2-di?uoro
ethane in an amount to provide about 0.2 theory of
20
?uorine and about 0.4 theory of chlorine.
16. A fuel for Otto cycle engines which consists es
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,398,281
Bartholomew __________ __ Apr. 9, 1946
2,784,160
Blaker _______________ __ Mar. 5, 1957
2,822,252
2,869,993
Boag et a1. ____________ .._ Feb. 4, 1958
Lyben _______________ __ Jan. 20, 1959
FOREIGN PATENTS
804,763
Great Britain ________ __ Nov. 19, 1958
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