U.S. patent number 3,753,670 [Application Number 05/051,363] was granted by the patent office on 1973-08-21 for hydrocarbon fuel compositions.
This patent grant is currently assigned to Shell Oil Company. Invention is credited to Isaac C. H. Robinson, Aart Strang.
United States Patent |
3,753,670 |
Strang , et al. |
August 21, 1973 |
HYDROCARBON FUEL COMPOSITIONS
Abstract
Liquid hydrocarbon fuel compositions, especially gasolines,
containing certain hydrocarbyl polyamines, effectively nullify
and/or inhibit fouling of vital parts of internal combustion
engines.
Inventors: |
Strang; Aart (Amsterdam,
NL), Robinson; Isaac C. H. (Chester, EN) |
Assignee: |
Shell Oil Company (New York,
NY)
|
Family
ID: |
10345781 |
Appl.
No.: |
05/051,363 |
Filed: |
June 30, 1970 |
Foreign Application Priority Data
|
|
|
|
|
Jun 30, 1969 [GB] |
|
|
32906/69 |
|
Current U.S.
Class: |
44/432; 44/333;
252/401 |
Current CPC
Class: |
C10L
1/2383 (20130101) |
Current International
Class: |
C10L
1/2383 (20060101); C10L 1/10 (20060101); C10l
001/22 () |
Field of
Search: |
;44/72,73 ;252/401 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Wyman; Daniel E.
Assistant Examiner: Shine; W. J.
Claims
We claim as our invention:
1. A method for reducing hydrocarbon exhaust gas emissions by
operating an internal combustion engine on a gasoline fuel
containing from 0.001 to 5 percent by weight of
N'-polyisobutenyl-N,N-dialkylpropylene-1,3-diamine wherein the
polyisobutenyl group has at least 50 and less than 200 carbon atoms
and each alkyl group of said dialkyl is unbranched alkyl of one to
three carbon atoms.
2. A method for reducing hydrocarbon exhaust gas emissions by
operating an internal combustion engine on a gasoline fuel
containing between 0.001 and 0.1 percent by weight of
N'-polyisobutenyl-N,N-dimethylpropylene-1,3-diamine wherein the
polyisobutenyl group has at least 50 and less than 200 carbon
atoms.
3. The composition of claim 1 in which the alkyl groups are
methyl.
4. The composition of claim 1 in which the amount of the diamine is
between 0.001 and 0.1 percent by weight.
Description
BACKGROUND OF THE INVENTION
The invention relates to fuel compositions having improved
properties. In particular, it relates to gasoline compositions
which effectively inhibit and/or prevent the fouling of the fuel
and inlet system of internal combustion engines.
One means of combating air pollution is to reduce the emission of
hydrocarbons by gasoline engines, due, inter alia, to crankcase
ventilation. This ventilation is necessary to prevent dilution and
contamination of the lubricating oil by unburnt or partly burnt
gasoline components leaking from the combustion chamber along the
piston and cylinder walls into the crankcase. The crankcase is
ventilated by a forced draft as a result of which components known
as blow-by gases, find their way into the atmosphere. To reduce
this type of emission, some engine manufacturers have provided the
engine with means for returning the mixture of blow-by gases and
air to the inlet system preceding the carburetor, for instance, to
the air filter. This measure, however, causes fouling of the fuel
and inlet system, which, in turn causes the engine to malfunction.
This tends to increase the concentration of unburnt and partly
burnt hydrocarbons in the exhaust gases.
It is possible to counteract fouling of the engine by incorporating
a minor amount of compounds with detergent properties into the
fuel. These compounds, however, if they are to be effective for
this purpose, must also possess good water-shedding properties. If
the water-shedding properties of a fuel additive are poor, the
additive promotes water pick-up and emulsion formation in the fuel.
Fuels containing such additives are, inter alia, difficult to
handle.
For non-surface vehicles such as supersonic aircraft, the fuels
(called aviation turbine fuels) have to meet very stringent thermal
stability requirements; they not only must absorb the large amounts
of heat generated, at high speeds, due to air friction, but must
also remain stable if they are to function properly.
These high temperatures further entail the risk of interreaction of
the hydrocarbon components present in the aviation fuel composition
with the resultant formation of products which may deposit on vital
engine parts. This can cause serious problems, such as clogging of
filters, control systems and fuel supply lines. Therefore, thermal
stability constitues one of the major problems of fuels for
supersonic aircraft.
Previous attempts have been made to solve these problems. As a
rule, however, the usual oxidation inhibitors have proven entirely
unsatisfactory. In certain cases inhibitors have even promoted the
formation of deposits. In other cases where the additives possessed
excellent antioxidant properties, they gave rise to the formation
of gasoline-water-emulsions when brought into contact with water.
For example, polyisobutenyl tetraethylene pentamine showed this
disadvantage when contacted with water.
SUMMARY OF THE INVENTION
A class of polyamine compounds has now been found which, when
incorporated as additives into the fuel in minor amounts,
effectively act to inhibit and prevent engine fouling. When added
to a gasoline, these polyamine compounds effectively counteract
engine fouling and specifically inhibit fouling of the carburetor
and to a certain extent also fouling of other parts of the fuel and
inlet system, such as valves and valve rods. They possess excellent
water-shedding properties and when incorporated into aviation
fuels, they stabilize these fuels against deterioration at high
tempeatures, and are able to minimize the formation of noxious
products in the fuel system of the aircraft engine.
The compounds concerned are polyamines wherein at least one
monovalent hydrocarbon group having at least 50 carbon atoms and at
least one monovalent hydrocarbon group having at most five carbon
atoms are bound directly to separate nitrogen atmos and wherein the
number of hydrogen atoms which are bound to nitrogen is smaller
than the number of nitrogen atoms present in the polyamine
molecule.
The invention therefore relates particularly to liquid hydrocarbon
fuel compositions comprising a major proportion of a fuel and a
minor proportion of one or more polyamines wherein at least one
monovalent hydrocarbon group having at least 50 carbon atoms and at
least one monovalent hydrocarbon group having at most five carbon
atoms are bound directly to nitrogen and wherein the number of
hydrogen atoms which are bound to nitrogen is smaller than the
number of nitrogen atoms present in the polyamine molecules.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The fuels to be used in the fuel compositions according to the
invention may be distillate fuels, flashed distillates or residual
fuels. Preferred are distillate fuels such as diesel fuels,
gasolines and aviation turbine fuels, the latter two being
particularly preferred.
Aviation turbine fuel can be defined as a hydrocarbon oil having a
Reid vapor pressure below 3 lb/sq. inch at 100.degree.F and a final
boiling point below 325.degree.C.
Gasoline can be defined as a mixture of hydrocarbons having a
boiling range determined according to ASTM method D 86 between
about 30.degree. and 210.degree.C.
It is very surprising that the additive according to the invention
shows such excellent water-shedding properties especially in
gasolines, since the water-shedding properties of very closely
related compounds are so poor that these compounds are unsuitable,
in this respect, as gasoline additives. If the performance of an
additive according to the invention, e.g., a reaction product of
one mole of a polyisobutenyl (PIB) chloride with one mole of
N,N-dimethylpropylene-1,3-diamine is compared with the performance
of a closely related compound, which, however, lies outside the
scope of the present invention, e.g., a reaction product of one
mole of the same polyisobutenyl chloride with one mole of
tetraethylenepentamine, it appears that although both compounds
have very good detergent properties, the former has excellent
water-shedding properties, while the water-shedding properties of
the latter are unacceptacle for a gasoline additive, since it tends
to form undesirable water-gasoline emulsions when contacted by
water.
Apparently, the fact that the terminal diamine structures of the
additives according to the invention are tertiary having a more
hydrophobic character rather than primary having a more hydrophilic
character as in the PIB-tetraethylenepentamine coupled with the
fact that the alkyl groups, according to the invention (.e.g,
methyl) are too small to significantly effect the polar nature of
the diamine, contribute, at least in part, to the advantageous use
of the additives according to the invention.
The polyamines which according to the invention are incorporated
into the fuel compositions (hereafter called the additives) may
contain, if desired, more than one of each of the above-mentioned
types of hydrocarbon groups. The monovalent groups may be bound to
the same nitrogen atom or to different nitrogen atoms. Here, by
monovalent hydrocarbon groups should be understood a monovalent
radical, built up substantially from carbon and hydrogen, in which,
however, dependent on the chosen method of preparation of the
additives, a minor amount of one or more other elements, e.g.,
halogen, may be present. Examples of suitable hydrocarbyl groups
are alkyl or alkenyl groups derived from alkanes or alkenes with a
straight or a branched carbon chain, which may carry aromatic or
cycloaliphatic hydrocarbon substituents. The hydrocarbon groups
having at least 50 carbon atoms are preferably non-substituted
alkenyl or alkyl groups, such as polyethylene groups, polypropylene
groups, polybutenyl groups and polyisobutenyl groups, regularly
branched being preferred. Additives containing less than 500 carbon
atoms are preferred as hydrocarbon groups having at least 50 carbon
atoms; particularly preferred are hydrocarbon groups having less
than 200 carbon atoms. Polyisobutenyl groups are preferred most as
hydrocarbon groups having at least 50 carbon atoms.
The hydrocarbon groups having at most 5 carbon atoms are preferably
alkyl groups with an unbranched carbon chain. Preferred are methyl,
ethyl and propyl. Methyl groups are preferred most.
In the additives according to the invention the number of hydrogen
atoms which are bound to nitrogen should be smaller than the number
of nitrogen atoms present in the additives. Preferred are additives
wherein the number of hydrogen atoms which are bound to nitrogen is
about half the number of nitrogen atoms present in the additive
molecule.
The polyamines acting as carriers of the monovalent hydrocarbon
groups in the additives according to the invention may be either
aliphatic or aromatic polyamines. Both diamines and higher amines
are suitable.
Examples of suitable diamines are ethylene-1,2-diamine,
propylene-1,2-diamine, propylene-1,3-diamine,
N,N-dimethylpropane-1,3-diamine, the butylene diamines and
benzene-1,4-diamine. Examples of suitable higher amines are the
polyalkylenepolyamines such as the polyethylenepolyamines, the
poly-propylenepolyamines and polybutylenepolyamines. Specific
examples of the polyethylenepolyamines are diethylenetriamine,
triethylenetetramine and tetraethylenepentamine,
pentaethylenehexamine and higher polyamines with a molecular weight
above 1000. As carriers of the monovalent hydrocarbon groups in the
additives according to the invention, alkylene diamines are
preferred, especially polymethylene-.alpha.,.omega.-diamine
particularly propylene-1,3-diamine.
The additives according to the invention may be prepared, for
instance, by allowing a polyamine which already carries the desired
number of monovalent hydrocarbon groups having at most five carbon
atoms to react with a halogen-containing hydrocarbon having at
least 50 carbon atoms in the molecule. One may very suitably start
from a chlorine-containing hydrocarbon obtained by chlorination
substitution of an alkene having at least 50 carbon atoms in the
molecule and a double bond in the terminal position whose
beta-carbon atoms carries a methyl group. The chlorination can very
suitably be performed with an amount of chlorine that is just
sufficient to convert the alkene into the corresponding alkenyl
chloride. One may start, for instance, from polyisobutene which -
in an inert solvent -- is converted, with a stoichiometric amount
of chlorine, into polyisobutenyl chloride. The reaction between the
halogen-containing hydrocarbon and the polyamine is carried out at
a temperature between 20.degree. and 200.degree.C, preferably in
the presence of an inert solvent. In the reaction between a halogen
containing hydrocarbon and a polyamine, hydrogen halide is formed
in addition to the desired additives. The hydrogen halide formed
combines with the polyamine used as starting material. Therefore,
unless special measures are taken, the polyamine has to be present
in large excess. Since it is desirable that the amount of polyamine
required for the preparation be kept as small as possible, it is
preferred that the reaction be carried out in the presence of a
hydrogen halide acceptor that differs both from the polyamine used
as starting material and from the additive formed. Examples of
hydrogen halide acceptors suitable for use in the preparation of
the present additives are, for instance, carbonates, bicarbonates,
oxides and hydroxides. Favorable results are obtained by using
sodium carbonate or potassium carbonate as the hydrogen halide
acceptor.
The molar ratio in which the halogen-containing hydrocarbon having
at least 50 carbon atoms in the molecule and the polyamine are
reacted depends on the number of such hydrocarbon groups one wishes
to introduce. For the preparation of additives according to the
invention in which substantially a single hydrocarbon group having
at least 50 carbon atoms in bound direct to one of the nitrogen
atoms of the polyamine, one preferably uses at most 2 gram
molecules of the starting polyamine per gram atom of
halogen-containing hydrocarbon.
If the additives according to the invention are prepared by a
process comprising the reaction of a halogen-containing hydrocarbon
having at least 50 carbon atoms in the molecule with a polyamine in
which one or more monovalent hydrocarbon groups with at most five
carbon atoms are bound direct to nitrogen, very suitable products
are produced from N,N-dimethylpropylene-1,3-diamine,
N,N-diethylpropylene-1,3-diamine, N,N-dipropylpropylene-1,3diamine,
N,N-dibutylpropylene-1,3-diamine,
N,N-dipentylpropylene-1,3-diamine, N-methylpropylene-1,3-diamine,
N-ethylpropylene-1,3-diamine, N-butylpropylene-1,3-diamine,
N-dienalpropylene-1,3-diamine and the like. Especially preferred is
N,N-dimethylpropylene-1,3-diamine.
Excellent results have been obtained by the reaction of
polyisobutenyl chlorides in which the average number of carbon
atoms amounted to about 91 and about 117 with an N,N-di
lower-alkyl-lower-alkylene-.alpha.,.omega. -diamine, specifically
N,N-dimethylpropylene-1,3-diamine, in which reaction about 1.3 gram
molecules of polyamine were used per gram atom of chlorine, present
in the polyisobutenyl chloride. In this way, additives according to
the invention were prepared wherein two lower-alkyl (one to four
carbon atom alkyls), such as methyl groups and substantially one
polyisobutenyl group having about 91 and 117 carbon atoms were
bound direct to nitrogen and wherein the number of hydrogen atoms
which were bound to nitrogen was substantially half the number of
nitrogen atoms present in the additive. These compounds, added in a
small amount, for example to an aviation turbine fuel, imparted to
that fuel stability against high temperatures, as was shown by the
performance of aviation turbine fuel compositions according to the
invention in a modified Fuel Coker Test. The aviation turbine fuels
used may have been freed of sulfur by means of hydrotreating, or
the sulfur compounds may have been converted by means of an acid
(e.g., sulfuric acid) treatment. When the compounds according to
the invention were added in a small amount to a gasoline, they
showed a high activity as cleanliness agents for the carburetor as
well as for other parts of the inlet system, such as the inlet
valves and the inlet valve rods. Moreover, their water-shedding
properties were excellent.
The concentration of the present additives in the fuel may vary
within wide limits. In general, the desired stabilizing effect is
obtained when the amount added is from 0.001 to 5%w preferably from
0.001 to 0.1%w. The additives may be added to the fuel as such or
in the form of a concentrate with a small amount of hydrocarbon
oil, such as a distillate fuel or lubricating oil.
In addition to a major amount of fuel and a minor amount of the
present additives, the fuel compositions according to the invention
may contain minor amounts of other additives by which the quality
of the fuel is further improved, such as agents improving the
ingition, scavenging agents, anti-icing additives, antioxidants,
conductivity improving agents, metal deactivating compounds.
Suitable metal deactivators are compounds having the formula
##SPC1##
wherein R represents a heterocyclic radical containing a -- C = N
-- group in a five-membered or six-membered ring and Y represents
hydrogen or a cyclic or acyclic substituent, or the two Y's
together with the ##SPC2## group form a cyclic structure. Examples
are compounds of the above formula, in which the R group represents
a thiazole, pyridine, quinoline or isopyrrole ring which may
contain one or more substituents, and in particular compounds
wherein this ring is attached to the nitrogen atom in the
alpha-position. A very active metal deactivator, in particular
copper deactivator, in this class of compounds is
1,3-di(2'-pyridyl)-iminoisoindoline.
Especially suitable metal deactivators, which may be used in the
fuel compositions according to the invention are compounds
belonging to the class of the
N,N'-disalicylidene-1,2-diaminoalkanes. Preferred in this class of
compounds is N,N'-disalicylidene-1,2-diaminopropane.
The amount of metal deactivators which may be present in the fuel
compositions according to the invention may vary within wide
limits, between about 0.0001 and 0.01%w.
Anitoxidants, in particular alkylphenolic anitoxidants such as
2,6-di-tert-butyl-4-methylphenol and
2,4-dimethyl-6-tert-butylphenol may also be present in the fuels
according to the invention, preferably between about 0.005 and
0.05%w.
Conductivity improving agents, which decrease the tendency for
self-inflammation during handling of fuels, in particular during
pumping of aviation turbine fuels, may also be incorporated in the
fuels. Suitable conductivity improving agents consist of a mixture
of the calcium or barium salt of dialkyl (e.g., dioctyl) sodium
sulfosuccinate, chromium salts of alkyl (e.g., C.sub.14 --C.sub.18)
salicylic acids and a copolymer of alkyl methacrylates (e.g.,
lauryl and/or stearyl methacrylates) and a vinyl-pyridine (e.g.,
2-methyl-5-vinyl-pyridino and/or 4 vinyl-pyridine).
The invention will be further characterized by the following
examples.
EXAMPLE I
Additive Synthesis
Two additives consisting of
N'-polyisobutenyl-N,N-dimethylpropylene- 1,3-diamine with different
molecular weights were prepared.
Additive 1: Polyisobutene with a molecular weight of 1280 was
dissolved in isooctance. After addition of a crystal of iodine to
this solution, chlorine was introduced - at room temperature -
until the color of the solution faded. Subsequently, the solvent
was vaporized. The residue contained 2.84%w chlorine, corresponding
to a mono-chloro-product.
A mixture of 123.2 g of polyisobutenyl chloride prepared in this
way, 60 ml toluene and 10 g pulverized potassium carbonate was
heated to 130.degree.C -- in a nitrogen atmosphere, with stirring
-- and subsequently, while the mixture was being stirred, 13.0 g
N,N-dimethylpropylene-1,3-diamine was added dropwise over a period
of 5 hours. Afterward, an additional amount of 4 g pulverized
potassium carbonate was added and the reaction mixture - while
being stirred - was kept at 130.degree.C for 15 hours. After
cooling down, the reaction product was taken up in a 60/80 gasoline
and washed with water until the washwater was free from chlorine.
The reaction product was isolated by vaporizing the solvent.
The product obtained weighed 124.5 g and had a nitrogen content of
1.24%w. It contained both secondary and tertiary amino nitrogens
and one carbon-to-carbon double bond.
Additive 2: Polyisobutene with a molecular weight of 1635 was
chlorinated, in the same way as described for additive 1, to a
product with a chlorine content of 2.0%w.
A mixture of 140.6 g of this polyisobutenyl chloride, 75 ml toluene
and 10 g pulverized potassium carbonate was heated to 130.degree.C
-- in a nitrogen atmosphere, with stirring -- and subsequently,
while the mixture was being stirred, 10.5 g
N,N-dimethylpropylene-1,3-diamine was added dropwise over a period
of five hours. After that, an additional amount of 4 g pulverized
potassium carbonate was added and the reaction mixture -- while
being stirred -- was kept at 130.degree.C for 15 hours. The
reaction mixture was finished in the same way as described for
additive 1.
The product obtained weighed 141.5 g and had a nitrogen content of
0.93%w. Analysis established it as being
N,N-dimethyl-N'-polyisobutenyl-propylene-1,3-diamine.
Additives A, B, C, and
D(N-polyisobutenyltetraethylenepentamines)
For comparison, four related compounds which, however, lie outside
the scope of the present invention, were prepared, starting from
tetraethylenepentamine and polyisobutenes with molecular weights of
950, 1280, 1380 and 1635, respectively. The preparation of these
additives was carried out in a way substantially the same as
described for the additives 1 and 2.
Additive E and F: Also for comparison, two commercial gasoline
dispersants were incorporated into the testing program.
Additive E is a reaction product of polyisobutenyl chloride, maleic
anhydride and tetraethylenepentamine.
Additive F is a mixture of alkylamine salts of alkylphosphoric
acids.
EXAMPLE II
The additives 1, 2, A, D, E and F were tested as gasoline additives
in a Sunbeam Talbot engine and in a Ford engine. The concentration
of the additives in the gasoline was 0.01%w. For comparison, the
two engine tests were also carried out with the same base gasoline
containing no such additives. As base gasoline, a premium grade
leaded gasoline was used.
Ford E 105 engine test: The extent of fouling of the carburetor was
determined in a Ford E 105 engine equipped with a Solex B 30 PSE
carburetor. The carburetor was of the standard design except for
the gas valve chamber having been bored and lined with a duralumin
insert. After the test, the fouling of the carburetor was
evaluated. In order to accelerate the formation of deposits, small,
accurately metered amounts of blow-by gas from the engine and
exhaust gas (representative of driving a car in heavy traffic) were
returned to the carburetor. The engine remained in operation for a
total test period of 90 hours according to a scheme providing for
operation in cycles consisting of running for 3.5 minutes at no
load and running for 30 seconds with partly opened gas valve under
conditions simulating driving on a road at normal load.
Sunbeam Talbot engine test: In this test, the inlet system fouling
is determined on the basis of fouling of the inlet valves and the
inlet valve rods. The test was carried out on a Sunbeam Talbot
engine with a piston displacement of 2264 cm.sup.3 , a compression
ratio of 6.45 : 1, and a maximum capacity of 70 bhp at 4000 rpm.
Before the test was started, the engine, including the two
carburetors, was cleaned whereupon the engine was kept in
continuous operation for 32 hours, at a speed of 1500 rpm, a
capacity of 15 bhp and a fuel consumption of 5.0 kg per hour. After
the test had been finished, the fouling of the inlet valves and the
inlet valve rods was evaluated.
The water-shedding properties of additive 1 and 2 and additives A-F
were determined in a test in which the fuel comprising 100 ppm
(parts per million) additive is shaken with distilled water at
ambient temperature under standard conditions. After adequate
settling, the water content of a sample taken at a specified depth
is determined by titration with Fischer reagent. The amount of free
water is calculated from the total water content and basic
solubility data.
The results of the engine tests and the water-shedding tests are
given in Table I. ##SPC3##
The compositions according to the invention are thus shown to
possess effective cleanliness properties and concomitantly
excellent water-shedding characteristics.
EXAMPLE III
Thermal Stability Test
The thermal stability of aviation turbine fuels containing additive
1 was tested according to a modified version of the ASTM/CRC Fuel
Coker Test, (ASTM D 1660). A test fuel reservoir and a preheater
different from those prescribed in the ASTM method were used
viz.:
1. As test fuel reservoir a stainless steel reservoir of 25 1
provided with a heating element was used wherein the fuel to be
tested could be brought in one hour to 275.degree.F and kept at
that temperature during the test in contact with the
atmosphere.
2. The preheater contained an aluminium preheater tube, which was
internally supported by a stainless steel tube. The outer tube of
the preheater was surrounded by a 3 cm thick layer of insulating
material.
Moreover, no in line micronic filter was present between the fuel
reservoir and the preheater.
The aviation turbine fuel compositions were tested for five hours
at a preheater fuel outlet temperature of 435.degree.F and a filter
temperature of 525.degree.F, maintaining a fuel temperature of
275.degree.F in the reservoir.
This modified version is considered to be a more severe test for
the fuel than the ASTM D 1660 test proper, in view of the high
preheater temperature and in view of the fact that the fuel to be
tested is in contact with air at a high temperature.
The drop over the filter in inches mercury and the rating of the
preheater tube deposits were determined as described in ASTM method
D 1660.
An aviation turbine fuels there were used an acid treated kerosene
and a hydrodesulfurized kerosene both with a Reid vapor pressure of
0.1 lb/sq inch at 100.degree.F and a boiling range from
150.degree.-250.degree.C.
Table 2 shows the results; tests 1, 2 and 6 are for comparison, and
not according to the invention. ##SPC4##
Thus, the inventive compositions showed markedly superior thermal
stability. Further, the addition of N,N'-disalicylidene-1,2-diamino
propane to the inventive compositions apparently enhanced their
effectiveness.
It is clear from the test results and preceding data that liquid
hydrocarbon distillate fuel compositions containing polyamines
according to the invention effectively counteract, nullify and/or
inhibit fouling of vital parts of internal combustion engines.
* * * * *