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BACKGROUND OF THE INVENTION
It is known that new, clean automotive engines operate more efficiently
than older ones that have accrued deposits of carbonized soil in the
cylinder areas. They also produce less pollutant gases in the form of
tailpipe emissions.
The functional problems of older engines have resulted in the use of more
highly refined gasoline/alcohol mixtures, detergent gasolines,
computerized fuel injection systems, and in the marketing of engine
injector solutions designed to solubilize the offending deposits. The
pollution problem has been partly resolved by the use of costly catalytic
converter equipment in a few countries. Worsening smog conditions and
related air pollution problems in metropolitan areas attest to the fact
that these approaches are relatively ineffective.
For many years there has been a search for engine additives that, when
injected directly into the upper cylinder areas, would exert a profound
cleaning effect and thus serve to remove carbonized varnishes and sludge
deposits that form on spark plugs, fuel orifices and cylinder walls. These
deposits inhibit the optimum burning of fuel. As such, they reduce
mile-per-gallon efficiency. Additionally, they tend to partly plug
critical orifices, interfere with spark gap operation of spark plugs,
cause piston sticking, and strongly promote the generation of partially
burned pyrolysis products during combustion of gasolines and diesel fuels.
Some fuel remains unburned. All these products are discharged into the
exhaust system. They include unburned hydrocarbons (aliphatics, cyclics
and aromatics), polycyclic alcohols, aldehydes and acids (sometimes
carcinogenic), oxygenated hydrocarbons of other types, and poisonous
carbon monoxide gas. These effluents are, to various degrees, further
oxidized by the catalytic converter. But significant amounts escape from
the tailpipe and those pose serious environmental hazards to humans,
animals and crops. All are included in the Federal Clean Air Act, as
amended, for this reason. Environmental Protection Agency regulations
under the act have imposed severe limitations on the airborne
concentrations of these vapors and particulates which, at this time, at
least seventy counties and air management districts cannot comply with
unless they would be willing to invite an intolerable degree of economic
distress.
Most of the discharged tailpipe vapors are capable of chemically reacting
with airborne nitrogen (II) oxide in ways that indirectly cause the
formation of excessive levels of tropospheric or ground-level ozone. This
gas is a strong irritant and possible proto-carcinogen that is directly
implicated in smog formation. The Clean Air Act regulations limit ozone
concentrations to 0.12 ppm and carbon monoxide levels to 9.0 ppm in air.
Test methods for determining product efficacy have been developed. They
have been used to obtain data on the relative cleaning efficiency of
individual chemicals, combinations of two or three chemicals that may show
synergistic activity, or on completely formulated concentrates. A well
regarded screening method uses the following procedure:
a. Carefully remove a spark plug from an engine.
b. Using an air knife, blow away any loose contamination. (Optional)
c. Weigh the spark plug.
d. Immerse it in the test liquid for five minutes at 77.degree. F.
(25.degree. C.).
e. Rinse momentarily in a volatile solvent, such as
1,1,1,-trichloromethane.
f. After or during drying, repeat the air knife removal of loose
contamination. (Optional)
g. Reweigh and note weight loss due to contaminant removal.
h. Visually compare with original spark plug condition, to establish
approximate per cent of contaminant removal.
i. Using a mild abrasive suspension/dispersion, a bronze buffing wheel or
other suitable process, remove any remaining contaminant without removing
any of the steel spark plug substance.
j. Determine weight loss due to 100% contaminant removal.
K. Calculate percent removal due to immersion in the test liquid and
compare with visual result of step h.
Various modifications of this procedure have been used to determine the
efficiency of over a hundred substances and blends, during product
development.
In this test it will be appreciated that no two spark plugs will give
identical results, even if they were used side by side for the same
service life in a given engine. Some deposits will be heavier, others will
be more intensely burned on, and some will exhibit higher degrees of
pyrolytic carbonization. This has made it necessary to differentiate
between spark plugs when testing by what is termed "the Cold Spark Plug
Immersion Test" (CSPIT). Three categories have been established:
a. Heavy baked-on varnish/sludge deposits.
b. Light, baked-on varnish/sludge deposits.
c. Highly carbonized, baked-on varnish/sludge deposits.
In the case of well-synergised, highly effective formulas of the subject
invention, CSPIT removal has been 90-100% for the light, baked-on
varnish/sludge deposits and 50-60% for the other two categories.
A large number of tests have been made on automotive engines. They have
been used to determine such attributes as:
a. Dynamic firing voltages (kV).
b. Specific exhaust gas concentrations (upstream from the catalytic
converter) including: i. Unburned hydrocarbon vapors (ppm). ii. Carbon
monoxide gas (ppm). iii. Oxygen gas (ppm). iv. Carbon dioxide gas (ppm).
c. Minimum smooth idling speed (rpm).
d. Increase in idling speed due to treatment (rpm).
e. Engine smoothness at idling speed due to treatment. (Substantive)
f. Degree of spark plug cleaning--by observation.
g. Reliability of the CSPIT, as a predictive test method.
Typical tests results are provided in the next section. They show that the
CSPIT method is a reliable predictive assay, removing about 90 percent as
much spark plug contaminants as are removed in the same time period by
what is termed "The Hot Engine Cleaning Test" (HECT).
A well regarded procedure for conducting the HECT assay is recited as
follows:
a. Select a car whose engine has been driven many thousands of miles on the
same set of spark plugs.
b. Remove one or more spark plugs and examine for amount and type of
varnish/sludge, after blowing off excess with an air knife.
c. Replace, using same spark plugs, or different test plugs.
d. Snap accelerate the engine to about 2000 rpm and run for two minutes on
gasoline.
e. Snap accelerate the engine to about 5000 rpm and run for a few seconds
to purge any loose carbonaceous matter out of the cylinders.
f. Conduct control tests.
Measure dynamic firing voltage (kV) on all cylinders, at idling rpm.
Measure tailpipe emissions at idling rpm.
Measure kV at low-cruise (1500 rpm).
Measure kV at high-cruise (2500 rpm).
Measure tailpipe emissions at high-cruise (2500 rpm).
g. Conduct product tests.
Connect product dispenser to engine.
Run engine at 2400-2500 rpm and add product. (Typically, add 260 grams of
product in five minutes).
Repeat steps d. and e.
Repeat tests listed under f.
h. Remove the one or more test spark plugs and determine percent sludge
removal.
Repeating the CSPIT procedure on cleaned spark plugs results in very little
additional contaminant removal; e.g. 5-15% more.
The cleaning ability and emissions reduction properties of the subject
composition have been evaluated in comparison with those of several of the
ten or twelve other cleaners currently on the market. It is significantly
better. Although these products make label claims promising to improve
engine performance and prolong the service life of catalytic converters by
reducing harmful emissions, in fact they demonstrate very limited
benefits. Consequently, the present market is small and rather static.
Advertising for the compounds is almost non-existent, and some firms
include them only to round out a line of automotive products.
Accordingly, the subject invention offers great advantages over the
products currently being marketed, and offers the first effective engine
cleaning composition compatible with fluorosilicone automotive gaskets.
SUMMARY OF THE INVENTION
The subject invention provides a composition of matter for dissolving
varnish and burned-on sludge in an internal combustion engine which
comprises (i) a ring-containing compound wherein the ring is composed of
five or six atoms consecutively linked, and (ii) hydrazine or an aliphatic
amine. The subject invention also provides a pressurized container which
comprises an amount of this composition and a gas propellant, as well as a
method for using the same.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1--Is a graph showing the cleaning efficiency of
N-methyl-2-pyrrolidone and n.butylamine blends on spark plug sludge in a
five (5) minute test. The dashed line represents the theoretical
(expected) curve. The solid line represents the actual (synergistic)
curve.
FIG. 2--Is a graph showing the clearing efficiency of tetrahydrofuran and
n.butylamine blends on spark plug sludge in a five (5) minute test. The
dashed line represents the theoretical (expected) curve. The solid line
represents the actual (synergistic) curve.
FIG. 3--Is a graph showing the cleaning efficiency of
N-methyl-2-pyrrolidone and diethylamine blends on spark plug sludge in a
five (5) minute test. The dashed line represents the theoretical
(expected) curve. The solid line represents the actual (synergistic)
curve.
FIG. 4--Is a graph showing the cleaning efficiency of 4-butyrolactone and
n.butylamine blends on spark plug sludge in a five (5) minute test. The
dashed line represents the theoretical (expected) curve. The solid line
represents the actual (synergistic) curve.
FIG. 5--Is a graph showing the cleaning efficiency of
N-methyl-2-pyrrolidone and isopropylamine blends on spark plug sludge in a
five (5) minute test. The dashed line represents the theoretical
(expected) curve. The solid line represents the actual (synergistic)
curve.
FIG. 6--Is a graph of cleaning efficiency of toluene and n.butylamine
blends on spark plug sludge in a five (5) minute test. The dashed line
represents the theoretical (expected) curve. The solid line represents the
actual (synergistic) curve.
FIG. 7--Is a graph of cleaning efficiency of dowanol EB and n.butylamine
blends on spark plug sludge in a five minute test. The dashed line
represents the theoretical (expected) curve. The solid line represents the
actual (synergistic) curve.
FIG. 8--Is a graph of cleaning efficiency of lubrizol 8163 mixture and
n.butylamine blends or spark plug sludge in a five (5) minute test. The
dashed line represents the theoretical (expected) curve. The solid line
represents the actual (synergistic) curve.
FIG. 9--Is a graph of cleaning efficiency of methyl t.butyl ether and
n.butylamine blends on spark plug sludge in a five (5) minute test. The
dashed line represents the theoretical (expected) curve. The solid line
represents the actual (synergistic) curve.
FIG. 10--Is a graph of cleaning efficiency of isopar E (mixed C.sub.7
isoparaffins--Exxon) and n.butylamine blend in a five (5) minute test. The
dashed line represents the theoretical (expected) curve. The solid line
represents the actual (synergistic) curve.
FIG. 11--Is a graph of residue removal at spark plugs after five minutes of
treatment with formulae nos. 66, 67, or 68. Formulae nos. 66, 67, and 68
are composites of:
20% N-methyl-2-pyrrolidone
10% Amine
61% Mixed C.sub.7 isoparaffinics
9% Methyl t.butyl ether
In formula 66 the amine is n.butylamine; in formula 67 the amine is
isopropylamine; and in formula 63 the amine is diethylamine. Type of
sludge or deposit:
A=Heavy crust of burned-on oil sludge
B=Light crust of burned-on oil sludge
C=Black, carbonized deposit of sludge
Av.=Average removal (%) of above sludges.
FIG. 12--Is a graph of residue removal at spark plugs after five minutes of
treatment with formulae nos. 69, 70, or 71. Formulae nos. 69, 70, and 71
are composites of:
21% N-methyl-2-pyrrolidone
5% Amine
4% Lubrizol No. 8166
61% Isopar C (mixed C.sub.7 isoparaffinics)
9% Methyl t.butyl ether
In formula 69 the amine is n.butylamine; in formula 70 the amine is
isopropylamine; and in formula 71 the amine is diethylamine. Type of
sludge or deposit:
A=Heavy crust of burned-on oil sludge
B=Light crust of burned-on oil sludge
C=Black, carbonized deposit of sludge
Av.=Average removal (%) of above sludges.
DETAILED DESCRIPTION OF THE INVENTION
The subject invention provides a composition of matter for dissolving
varnish and burned-on sludge in an internal combustion engine which
comprises (i) a ring-containing compound wherein the ring is composed of
five or six atoms consecutively linked, and (ii) hydrazine or an aliphatic
amine.
The atoms in the ring may be carbon, nitrogen, oxygen, or sulfur, and the
compound may comprise straight or branched chains attached to one or more
of the atoms.
A large number of pure solvents have been tested by the CSPIT procedure.
Many are classified as extremely strong solvents by such tests as
Kauri-Butanol, Solubility Product, and so forth. With the exception of
three aliphatic amines and hydrazine, none of the solvents showed any
significant sludge removal activity.
Over fifty two component blends, many of them containing the aliphatic
amines, were then tested by the CSPIT method. Surprisingly, many of the
aliphatic amine blends were found to exhibit synergistic activity,
removing the varnish/sludge deposits on spark plugs with outstanding speed
and efficiency. In the case of the synergistic compositions, most of the
removal values for specific blends were substantially greater than would
have been predicted from a straight line relationship, using the removal
values of the individual solvents. For example, a blend of 75%
N-methyl-2-pyrrolidone and 25% n.butylamine showed 97 percent removal of
light, baked-on varnish/sludge deposits. However, only a 26 percent
removal would have been predicted, based upon a weighted average of the
removal ratings of the pure components.
When these synergistic pairs were incorporated into finished concentrates,
the removal abilities of the concentrates appeared to be a close match to
the predictable or theoretical value if no additional synergistic solvents
were added. For example, a concentrate containing 25% of a synergistic
blend with an 80 percent removal rating might have a removal efficiency of
20 percent if the diluent was a non-synergistic solvent, such as an
iso-octane/iso-propanol blend.
During the testing, various simple, aliphatic amines were couple with one
of the following compounds:
______________________________________
Ring Compound Skeletal Structure
______________________________________
N-Methyl-2-pyrrolidone (M-Pyrol)
##STR1##
Tetrahydrofuran (THF)
##STR2##
4-Butyrolactone
##STR3##
Toluene
##STR4##
______________________________________
All are very strong solvents in normal circumstances. None were
particularly effective against burned-on varnishes. Each produced strong
synergism with the amines, at 5-15% amine or higher for the heterocyclics,
and 20% or higher for the toluene/n.butylamine blend.
The degree of varnish/sludge removal, versus binary composition has been
carefully determined for ten pairs of solvents, one of which was a simple
primary amine. Synergism was found in seven of the pairs.
(Counter-synergism, or negative synergism was also determined for some
synergistic binaries--especially at high amine compositions.) Such
solvents as ethylene glycol n.butyl ether, methyl t.butyl ether, isomeric
iso-octanes, and a well known top cylinder lubricant mixture: Lubrizol
#8163 (Lubrizol, Inc.) failed to produce synergistic effects with simple
aliphatic amines, except for a slight effect with Lubrizol #8163. This may
be due to the presence of 20 percent mixed xylenes in the Lubrizol #8163
composition.
(See the table titled Analysis of Figures in the Experimental Detail
Section)
The binary system of N-methyl-2-pyrrolidone and n.butylamine demonstrated
the highest varnish/sludge removal efficiency (to 97 percent) of those
tested.
The binary system on N-methyl-2-pyrrolidone and iso-propylamine was almost
as high (to 85 percent) and was later found to be at least as effective as
the N-methyl-2-pyrrolidone and n.butylamine couple when diluted into the
finished concentrate. However, isopropylamine is extremely flammable,
smokes in air, is in short supply, is very caustic and is highly volatile.
These properties suggest against commercial applications.
In a preferred embodiment of the subject invention, the composition of
matter for dissolving varnish and burned-on sludge further comprises an
amount of water effective to increase the dissolving of varnish and
burned-on sludge. Most preferably, the water comprises less than about
1.0% of the composition.
The extraordinary cleaning performance of the N-methyl- 2-pyrrolidone and
n.butylamine couple remained a mystery until it was discovered that the
supply container of n.butylamine contained product that was slightly
contaminated with water. Control studies using fresh, high grade
n.butylamine gave somewhat lower cleaning results. The tramp water was
considered to allow the solvent to pass partially into the ionic form:
CH.sub.3 (CH.sub.2).sub.3 --NH.sub.3.sup.+ OH.sup.- (n.butylammonium
hydroxide) and more fruitfully develop the high pH value, caustic
qualities that are sought after in water-based oven cleaners, charcoal
grill cleaners and similar products.
After this, water was deliberately added to formulae, with the finding that
it did indeed improve the cleaning ability of both binary synergistic
pairs and finished products.
However, only about one per cent water, at most, could be included in
finished products before incompatibility resulted and the concentrate
would separate into two liquid phases; one richer in water content than
the other. This is mainly due to the extreme insolubility of water and the
isomeric iso-octanes.
In order to gain the benefits of adding additional water, the use of a
simple co-solvent was tested. Such items as methanol, ethanol,
iso-propanol and n.propanol were tested. Iso-propanol was eventually
selected because it is non-poisonous, available without denaturants or
payment of special taxes and readily available from a multiplicity of
suppliers. It was used at 10 percent or so of the final formula and thus
served to approximately double the amount of water that could be
incorporated into the concentrate without phase separation. It is also
thought to aid the combustion process somewhat, as in the case of
"gasohol" type blends of predominantly gasolines and ethanol. Out of these
various studies it became quickly apparent that water could be considered
a vital third component of the synergistic systems already described.
It is also preferred that the composition of matter comprises a suitable
engine fuel. In optimally applying the teaching of the invention, a
synergistic pair of cyclic and amine compounds is prepared, and to this is
added about 50 percent or more of isooctanes or similar engine fuel. About
10 percent of isopropanol or similar simple alcohol is then added.
De-ionized water must be added in an amount of about 1 percent as the
third member of synergistic varnish/sludge remover triad. This is best
done by completing a concentrate batch except for water addition, then
removing about 10 percent into a separate vessel. The main batch is then
titrated with successive amounts of water until incipient phase separation
occurs, as evident by the generation of haziness, which takes several
minutes to dissipate on further stirring. At that point the separated 10
percent portion is added back in and the batch is complete. Because it is
sensitive to moisture and carbon dioxide in the ambient air, as well as
flammable, it should be stored in a sealed tank brief periods until used
in the aerosol manufacturing operation.
In another embodiment, in the composition of matter, the ring-containing
compound and the hydrazine or aliphatic amine are in synergistic amounts.
Often it is preferred that the aliphatic amine is a primary or a secondary
amine, and that the amine comprises from about 5% to about 75% of the
composition. More preferably, the amine is a C.sub.1 -C.sub.8 primary
amine, or is a secondary amine having C.sub.1 -C.sub.8 branches.
It is also preferred that the amine is selected from the group consisting
of n-butylamine, triethylamine, diethylamine, and isopropylamine, and the
ring-containing compound is selected from the group consisting of
N-methyl-2-pyrrolidone, tetrahydrofuran 4-butyrolactone, toluene, and
xylene. Normally, the weight ratio of the ring-containing compound to the
aliphatic amine is from 4:96 to 96:4.
The binary synergistic pairs of cyclic and simple amines work fairly well
without the need for added water. Some of this activity may be due to
small amounts of tramp water normally present in the commercial materials,
or incorporated from exposure to air during compounding and testing
procedures. Ordinary methods of analysis (as the classical Karl Fischer
Method) cannot be used to determine this tramp water, due to interferences
from the active cyclics and amines, as a general rule.
On the basis of the more that 230 studies performed to date on pure
materials, binary blends and concentrates it has been found that synergism
takes place between five and six membered single heterocyclic ring
compounds, as well as six membered aromatic ring systems, when these
materials are mixed with simple aliphatic primary and secondary amines, of
C.sub.2, C.sub.3 and C.sub.4 complexity, at ratios that extend from about
4:96 to about 96:4, depending upon the particular blend. The binary of
hydrazine and water also gives excellent results.
The synergistic effect of the N-methyl-2-pyrrolidone/n.butylamine couple
and the N-methyl-2-pyrrolidone/diethylamine couple is presented in FIGS. 1
and 2.
It will be apparent that a wider array of synergistic binaries could be
developed on the basis of further testing. Adding alkyl groups to the ring
compounds, or to the simple amines should merely introduce a "moiety
diluent" effect. For example, N-n.butyl-2-pyrrolidone and n.octylamine
would be expected to exhibit synergism, but to a lesser degree than that
of the simpler counterparts. The beneficial effect of using
iso-propylamine instead of n.butylamine is shown by the comparison of
varnish/sludge removal of Formulae 72 and 73.
______________________________________
FORMULA 72
FORMULA 73
______________________________________
INGREDIENTS*
N-Methyl-2-pyrrolidone
20% 20%
n.Butylamine 4% --
iso-Propylamine -- 4%
Lubrizol 8166 Mixture
4% 4%
(Lubrizol, Inc.)
Isopar C (Exxon, Inc.)
62% 62%
Mainly iso-C.sub.8 -paraffinics
Methyl-t.butylether
10% 10%
CSPIT RESULTS
Removal of light varnish/
35% 75%
sludge
Removal of carbonized
20% 55%
varnish/sludge
______________________________________
*Tramp water content of finished concentrates estimated as about 0.3%.
A comparison van be made to show the beneficial effect of deliberately
adding water to another pair of N-methyl-2-pyrrolidone/n.butylamine
formulae; e.g. Formulae 69 and 82.
______________________________________
FORMULA 69
FORMULA 82
______________________________________
INGREDIENTS*
N-Methyl-2-pyrrolidone
20.5% 20.0%
n.Butylamine 5.0% 5.0%
Water 0.3% 1.4%
Lubrizol 8166 Mixture
4.0% 4.0%
(Lubrizol, Inc.)
Isopar C (Exxon, Inc.)
61.2% 58.8%
Mainly iso-C.sub.8 -paraffinics
Isopropanol (Anhydrous)
-- 10.8%
Methyl t.butylether
9.0% --
pH Value (25.degree. C.)
12.6 13.0
CSPIT RESULTS
Removal of heavy varnish/
50% --
sludge
Removal of light varnish/
90% 93%
sludge
Removal of carbonized
50% 60%
varnish/sludge
REDUCTION OF TAILPIPE EMISSIONS**
Unburned hydrocarbon fuel
81% & 81% 91%, 52% & 92%
Carbon Monoxide 88% & 86% 65%, 57% & 90%
______________________________________
*Tramp water of Formula 69 estimated as 0.3%. (None was specifically
added.)
**See more detailed summary sheet that follows.
The summary sheet of data, found in the Experimental Detail Section, on a
number of automotive tests shows that in all cases the emission levels of
noxious unburned hydro-carbon fuels and carbon monoxide are reduced.
Maximum reductions were to 1.5 ppm for unburned hydrocarbons and 0.01 ppm
for carbon monoxide, showing the potential of these synergised products.
The scope of the invention will be readily apparent to those skilled in the
art, from the above description and examples, which are included to
further exemplify the methods of practicing the invention and are not
intended to be of limiting scope.
The composition of matter may further comprise an additive selected from
the group consisting of lower alkyl alcohols, lubricants, and ethers.
Lower alkyl alcohols are to include but not limited to C.sub.1 to C.sub.8
aliphatic alcohols.
In another embodiment, the composition of matter further comprises ammonia
or ammonium hydroxide, more preferably in combination with triethylamine.
Most preferably, the triethylamine is present in a concentration of
greater than about 10%.
The subject invention provides in a most preferred embodiment, a
three-component, mutually synergistic blend, having a high pH value
(typically 13.0) and high alkalinity which, when dissolved in a suitable
fuel base, may be injected into engines to perform a cleaning function
that is dramatically superior to that of any known product.
In one embodiment, a delivery system is required to inject the undiluted
product directly into the upper cylinder areas so that it can contact and
dissolve the various baked-on partly carbonized varnishes and sludge
deposits that are so harmful. To do this, the concentrate is filled into
an aerosol container, after which the container is fitted with a suitable
valve, sealed and pressurized with nitrogen gas. A supplementary transfer
system, consisting of a tube and other components, is used to inject the
produce into the engine while it is operating at approximately 2000 rpm.
One such system for supplying the pressurized composition is described in
U.S. Pat. No. 4,807,578, issued Feb. 28, 1989.
The three-component, mutually synergistic blend is preferably a solution of
a simple, five or six-membered heterocyclic ring compound with a simple
primary amine, to which a small amount of deionized water is added to
enhance potency. This mixture comprises about 25 percent of the formula.
Since it is necessary to have the engine running during the approximately
five minute injection and cleaning phase, a suitable fuel must be included
in the formula. Various gasolines may be used, but for a higher Octane
Rating and better product uniformity, the use of a specific commercial
mixture of predominantly isomeric isooctanes is recommended. The final
required ingredient is a simple aliphatic alcohol, used as a co-solvent to
enable the inclusion of a somewhat higher level of water before phase
separation occurs. Up to about ten percent of other ingredients may be
included as lubricants or for other non-essential purposes. Finally,
nitrogen has been found to be the optimum pressurizing gas, since it is
not subject to vapor-lock problems during dispensing, provides any desired
legal pressure, is useful at a fraction of one percent (thus minimally
diluting the concentrate), and is very safe and inexpensive to fill and
use.
The subject invention also provides for a pressurized container comprising
an amount of the above-described composition and a gas propellant.
The propellant may be selected from the group consisting of nitrogen, air,
helium, carbon dioxide, and nitrous oxide, and preferably is nitrogen. The
container is then pressurized to 25-180 psi-g.
Nitrogen has been selected as the preferred propellant. It is inexpensive,
non-toxic, and develops the more preferred pressure range of about 40-120
psi-g at 70.degree. F., according to the quantity added per can, and does
not unduly dilute the concentrate. Additionally, it prevents the
vapor-locking found with certain alternative propellants.
One preferred container comprises about 35.0% by weight of
N-methyl-2-pyrrolidone; 15.0% by weight of diethylamine; 49.0% by weight
of iso-C.sub.8 -paraffinics; 0.5% by weight of deionized water; and 0.5%
by weight of nitrogen gas.
Also provided for is a container which comprises about 35.0% by weight of
N-methyl-2-pyrrolidone; 15.0% by weight of isopropylamine; 48.5% by weight
of iso-C8-paraffinics; 1.1% by weight of deionized water; and 0.4% by
weight of nitrogen gas.
The container may also comprise about 30.0% by weight of tetrahydrofuran;
10.0% by weight of n.butylamine; 45.0% by weight of iso-C.sub.8
-paraffinics; 0.5% by weight of deionized water; 4.0% by weight of
lubrizol 8166 mixture; 10.0% by weight of methyl t.butylether; and 0.5% by
weight of nitrogen gas.
Yet another container comprises about 25.0% by weight of butyrolactone;
12.0% by weight of n.pentylamine; 41.0% by weight of unleaded gasoline;
1.0% by weight of deionized water; 10.0% by weight of isopropanol
(anhydrous); 10.0% by weight of methyl t.butylether; 0.5% by weight of
lubricating oil; and 0.5% by weight of nitrogen gas.
Another container comprises about 18.0% by weight of toluene; 22.0% by
weight of n.butylamine; 10.0% by weight of unleaded gasoline; 44.3% by
weight of n.C.sub.9-10 -paraffinics; 1.2% by weight of deionized water;
3.9% by weight of methanol (99.5%); and 0.6% by weight of nitrogen gas.
A further container comprises about 30.0% by weight of hydrazine
monohydrate; 15.0% by weight of N-methyl-2-pyrrolidone; 42.5% by weight of
iso-C.sub.8 -paraffinics; 12.0% by weight of ethanol (anhydrous); and 0.5%
by weight of nitrogen gas.
Another preferred container comprises about 16.0% by weight of mixed
isometric xylenes; 24.0% by weight of diethylamine; 49.0% by weight of
unleaded gasoline; 0.8% by weight of deionized water; 9.7% by weight of
n.propanol; and 0.5% by weight of nitrogen gas.
A further container comprises about 5.0% by weight of
N-methyl-2-pyrrolidone; 10.0% by weight of triethylamine; 18.0% by weight
of isopropanol (anhydrous); 4.0% by weight of xylene-based lubricant;
10.0% by weight of toluene or xylenes; 49.3% by weight of
iso-(C.sub.7-8)-isoparaffins; 3.0% by weight of ammonium hydroxide (28%);
and 0.7% by weight of nitrogen gas.
Finally, a container which comprises about 10.0% by weight of
N-methyl-2-pyrrolidone; 22.2% by weight of 2-pyrrolidone-1-hydrate; 30.0%
by weight of xylenes or toluene; 4.0% by weight of isopropanol
(anhydrous); 15.0% by weight of methyl t.butylether; 2.0% by weight of
ammonium hydroxide (28%); 1.7% by weight of deionized water; 0.5% by
weight of dowfax 2Al surfactant; 14.0% by weight of triethylamine; and
0.6% by weight of nitrogen gas is provided for. by weight of
triethylamine; and 0.6% by weight of nitrogen gas is provided for.
The subject invention also provides a method of dissolving varnish and
burned-on sludge in an internal combustion engine which comprises mixing
the subject composition with suitable engine fuel to form an admixture and
contacting the fuel-exposed areas of the engine with the admixture under
conditions such that the varnish and burned-on sludge is dissolved. This
may be accomplished by any of the methods known to one skilled in the art,
and is to include, but is not limited to, applying the admixture in an
aerosol form directly to the fuel line without seriously disturbing the
engine's normal fuel line connection, or by forming the admixture in the
gas tank using fuel contained therein.
It is recognized that variations in these and related formulas and factors
could readily be made within the concepts taught herein. Hence, the
invention is intended to be limited only by the scope of the claims and
the reasonable equivalents thereof. The following Experimental Detail
section is provided to better illustrate the subject invention, and is not
to be construed as limiting the subject invention.
Experimental Detail
EXAMPLE 1
An automotive engine injector type cleaner having the composition:
______________________________________
N-Methyl-2-pyrrolidone
35.0%
Diethylamine 15.0%
iso-C.sub.8 -paraffinics
49.0%
De-ionized Water 0.5%
Nitrogen Gas 0.5%
______________________________________
was prepared by mixing the first three ingredients and then adding water to
the point of incipient phase separation. After that the concentrate was
packaged and the dispenser gassed with nitrogen propellant. The pH value
of the concentrate was 12.5 at 25.degree. C. Removal of varnish/sludge
spark plug contaminants by the CSPIT test was 55% for heavy soils, 98% for
light soils and 40% for carbonized soils.
EXAMPLE 2
An automotive engine injector type cleaner having the composition:
______________________________________
N-Methyl-2-pyrrolidone
35.0%
iso-Propylamine 15.0%
iso-C.sub.8 -paraffinics
48.5%
De-ionized Water 1.1%
Nitrogen Gas 0.4%
______________________________________
was prepared as above. The pH value of the concentrate was 12.8 at
25.degree. C. before adding the water, and 13.4 at 25.degree. C. after
adding the water. Removal of varnish/sludge spark plug contaminants by the
CSPIT test was 55% for heavy soil, 98% for light soils and 60% for
carbonized soils. This formula was judge higher in pH and more effective
in soil removal than Formula 1.
EXAMPLE 3
An automotive engine injector type cleaner having the composition:
______________________________________
Tetrahydrofuran (THF)
30%
n.Butylamine 10%
iso-C.sub.8 -paraffinics
45%
De-ionized Water 0.5%
Lubrizol 8166 Mixture
4%
Methyl t.butylether
10%
Nitrogen Gas 0.5%
______________________________________
can be prepared by mixing the ingredients, except water and nitrogen, then
adding the water to the point of incipient phase separation. Package and
gas with nitrogen propellant. The pH value of the concentrate is 12.6 at
25.degree. C.
EXAMPLE 4
An automotive engine cleaner of the injection type having the composition:
______________________________________
Butyrolactone 25%
n.Pentylamine 12%
Unleaded Gasoline 41%
De-ionized Water 1%
Iso-propanol (Anhydrous)
10%
Methyl t.butylether 10%
Lubricating Oil 0.5%
Nitrogen Gas 0.5%
______________________________________
can be prepared by combining all of the ingredients except water and
nitrogen gas, then adding the required amount of water. Package and gas
with nitrogen propellant.
EXAMPLE 5
______________________________________
Toluene 18.0%
n.Butylamine 22.0%
Unleaded Gasoline 10.0%
n.C.sub.9-10 -paraffinics
44.3%
De-ionized Water 1.2%
Methanol - 99.5% 3.9%
Nitrogen Gas 0.6%
______________________________________
can be prepared by combining all the ingredients, but adding the water
last; then gassing with the nitrogen propellant
EXAMPLE 6
An automotive engine cleaner of the injection type having the composition:
______________________________________
Hydrazine Monohydrate
30.0%
N-Methyl-2-pyrrolidone
15.0%
iso-C.sub.8 -paraffinics
42.5%
Ethanol* (Anhydrous)
12.0%
Nitrogen Gas 0.5%
______________________________________
can be prepared by mixing items except hydrazine; then adding hydrazine
and gas.
EXAMPLE 7
An automotive injector type cleaner having the composition:
______________________________________
Mixed Isomeric Xylenes
16.0%
Diethylamine 24.0%
Unleaded Gasolines 49.0%
De-ionized Water 0.8%
n.Propanol 9.7%
Nitrogen Gas 0.5%
______________________________________
can be prepared by combining all the ingredients except water and nitrogen,
then adding the water and gassing with nitrogen propellant.
EXAMPLE 8
An automotive engine injector type cleaner having the composition:
______________________________________
N-Methyl-2-pyrrolidone
5.0%
Triethylamine 10.0%
Isopropanol (Anhydrous)
18.0%
Xylene-based lubricant
4.0%
Toluene (or Xylenes) 10.0%
iso-(C.sub.7, C.sub.8)-isoparaffins
49.3%
Ammonium Hydroxide | | |
