Note: Descriptions are shown in the official language in which they were submitted.
The present invention relates to an energy-saving fuel additive
which is suitable for jet, gasoline, and diesel engines, and which is also
suitable for use as an additive for domestic heating and light industrial
o.ils (#2 and ~3) and bunker or residual fuels (#4, 5, and 6)o Accordingly
the present invention provides a fuel additive suitable for internal com-
bustion, jet and diesel engines consisting of an active ingredient formula-
tion comprising a mixture of picric acid and ferrous sulfate in a mixed sol-
vent of lower alcohol, toluene, and water, the picric acid being present in
an excess by weight over the ferrous sulfate. me general designations or
1~ gradations of fuel oils are as accepted by the American Society of Testing
~la~crials, Philadelphia, Pennsylvania, and cited in Encyclopedia of Chemical
Teclmology II,Volume 15, page 81 (1968~ Wiley-Interscience~.
A preferred solvent suitable for use is a combination of an alkyl
benzene, for example toluene, and a lower alcohol, for example isopropanol.
Operable substitutes for isopropyl alcohol, although not preferred are eth-
anol and methanol together with water and the two may be used in a composite
relationship. The combination specially may also include a minor amount of
nitrobenzene as well as a particulate reducer such as a long chain tertiary
amine (Primene 81R).
In a particular embodiment the present invention provides a fuel
additive consisting of an active ingredient formulation comprising a mixture
of picric acid and ferrous sulfate in a mixed solvent of lower alcohol,
alkyl benzene and water, the picric acid being present in an excess by weight
over the ferrous sulfate.
In a further aspect the present invention provides a method for
treating fuels which comprises adding thereto ~o each United States gallon an
additive/fuel comprising a mixture of picric acid and ferrous sulfate in a
mixed solvent of lower alkanol, alkyl benzene and water in a dosage of about
l:l,O00 to 1:2,000 additive to fuel, the picric acid being present in an ex-
cess by weight over the ferrous sulfate.
A preferred additive mix or concentrate denotes MSX Mix useful for
bul~ addition is as follows for one gallon:
-1-
. ~ ~
U.S. Gallon Imperial Gallon
Most Preferred Range Most Preferred Range
Ferrous sulfate 1.4 g .08 ~ g 1.7 g 0.1 - 1.7 g
Picric acid (trinitrophenol~ 45.0 g 2.8 - 45.0 g 54.0 g 3.5 -54.0 g
Toluene 2.4 kg 2.4 - 1.0 kg 2.9 kg 2.9 - 1.2 kg
Isopropyl alcohol 1.0 kg l.0 - 2.4 kg 1.2 kg 1.2 - 2.9 kg
Nitrobenzene 2.7 g .08 - 2.7 g 3.2 g 0.1 - 3.2 g
Long chain amine; e.g.,
tertiary dodecylamine 1.7 g .2 - 1.7 g2.0 g .24- 2.0 g
Water Balance salance Balance Balance
In the solvent the preferred relationship of toluene and isopropyl alcohol is
about 2:1 by weight.
Additionally, where heavy oils are involved as with bunker and
residual fuels ~#4, 5, and 6) a preferred formulation is as follows for one
gallon:
U.S. Gallon Imperial Gallon
Most Preferred Range Most P_eferred Range
~errous sulfate 4 g 4 - 5.6 g5 g5 - 7 g
Picric acid ~trinitrophenol) 8 g 8 -12 g lO g 10 -15 g
Toluene 4 kg 4 - 5.6 kg 5 kg 5 - 7 kg
Isopropanol .8 kg .8 - 1.2 kg 1 kg 1 - 1.5 kg
Long chain amine; e.g.,
tertiary dodecylamine .2 g .2 - 1.7 g .24 g .24 - 2.0 g
l~ater Balance Balance Balance Balance
The MSX ~lix is utilized for dosage to fuels in the ratio of
- 1:1,000 to 1:2,000 with a preferred dosage of 1:1600 parts by volume.
In the aforesaid formula which is set out for United States and
Canadian use, it is noted that the most preferred range in the MSX Mix is at
or near the highest range given, which gives a more active composition. In
addition, where nitrobenzene is utilized and especially for bunker fuels, the
top values of the range are near the delimiting value presently set Ollt by
Energy Research and Development Administration for NOx emissions.
-- 2 --
7~
A catalytic action occurs in the binary active ingredient due to
the presence of the metallic ion Fe in the composition, causing the sligh~ly
heavier and less volatile ends to burn completely, thus increasin~ the energy
and decreasing the emissions of raw hydrocarbons from the exhaust.
The prior art statement for the present invention is set out as
follows:
a) Art Relating to picric acid:
United States Patent 928,803 Selden teaches at column 1 use of
picrates of fused ring compounds such as naphthalene in a solvent selected
from alcohols, benzene, and acetone.
United States Patent 3,294,501 Kawahara notes the use of picric
acid at column 1 as a lead appreciator.
United States Patent 3,434,814 Dubeck speaks of the reduction of
hydrocarbon emission from internal combustion engines by operating the gasoline
containing ortho-substituted aromatic nitro compounds and prefers picryl ace-
tate.
b) Art Bearing on Ferrous Sulfate:
. . ~
United States Patent 3,002,826 Norris as an additive incorporates
preferably aluminum sulfate and other salts, both inorganic and organic, to
reduce vanadium deposition which causes corrosion and deposits.
United States Patent 3,348,932 Kukin at column 2 states that a small
percentage of iron salts may be used as part of a sal-t combination as a combus-
tion aid in domestic furnaces, diesel equipment, jet engines, etc., -to force
combustion of the fuel to ~inal products, such as carbon dioxide and water.
c) Art Pertaining to the Solvent:
~ = _ .
United States Patent 914,624 Winand, at page l, column 2, mentions
the use of nitrobenzene as "an oxygen-bearer."
United States Patent 1,423,050 Tunison, at column 2, line 103,
mentions nitrobenzol or nitrobenzene as an explosion promoter for internal
combustion engines and diesel engines.
United States Patent 4,002,435 Wenzel illustrates a water-in-oil
emulsion of hydrocarbons, water, and an alcohol suitable for injection methods
as noted in column 2.
The energy-saving compositionsand method of treating fuels set out
in the present invention differ from the above-cited prior art. Primarily
this invention lies in a novel mixture of active ingredients; namely, picric
acid t2,~,6-trinitrophenol) and ferrous sulate ~FeS0~1). These constitute
the active ingredients of the present composition utilizing picric acid in the
majority amount. In a preferred bulk composition, the amount of picric acid
in a United States gallon ranges from 2.~ - 45.36 grams and the ferrous sulfate
.08 - 1.36 grams. Thus, as has been stated as to the thrust of use, the picric
acid provides the major oxidizing component of the composition and the ferrous
lron in the ferrous sulfate provides the catalytic action. Nitrobenzene is
used primarily as a solvent and has a secondary use as an auxiliary oxidant.
The active ingredients, as well as the solvents of the present invention, have
a unique utility over compositions having other salts in that this composition
is compatible with the "catalytic converter" containing platinum and paladium
compounds which has been mandatory in the United States for new cars since
1975. Thus, it is an appreciator for "no lead" fuel used in such cars.
2Q The Active Ingredients of the present invention are picric acid and
ferrous sulfate.
Picric acid, also known as 2J4,6-trinitrophenol, is used in this
invention as a strong oxidizing agent.
Ferrous sulfate is used for catalytic action in combination with the
superior amount of picric acid noted above. The Fe ion is readily oxidized
to ferric or reduced to Fe. The compound is included since i~ represents a
metal compound which can be oxidized and then retransformed into the lower
oxidized state or first transformed to ferric and then retransformed to
ferrous. The presence of the ferrous sulfate salt lends greater activity to
the composition than would be expected when considering its minor percentile
inclusion in the composition and thus may be viewed as a catalytic agent.
Also, and quite importantly, iron sulfate has shown less corrosion on iron
than such compounds as nickel sulfate) nickel nitrate, and cadmium sulfate
in comparative testing. Additionally, the combination of picric acid and
ferrous sulfate may be termed true synergistic mixture of other additives.
In all cases, a catalytic action takes place due to the presence of a ferrous
ion in the compound. The slightly heavier and less volatile ends are com-
pletely burned, thus increasing the energy and decreasing the emissions of
raw hydrocarbons from the exhaust. Without the catalytic complete combustion
of the fuel, the heavy ends condense on the comparatively cooler cylinder
walls, eventually manifesting themselves as crankcase dilution elements, gum,
slud~e, etc. Therefore, the addition of the produc~ to the fuel not only
increases the energy output but also contributes to the more efficient and
longer life of the lubricating oil at the same time giving a clean carbon and
gum-free internal combustion engine.
Other Ingredients may be chosen from the group consisting of:
a) Alkylbenzenes. Of the alkyl ben~enes possible, toluene, ortho-,
meta-, and paraxylenes are preferred~ and the mesitylenes are operable.
b~ Alkanol. Of the lower alkanols, isopropanol is utilized in the MSX
~O Mix as solvent of choice. Methyl and ethyl alcohols are operable but not as
effective.
c) Nitrobenzene. This compound, as in the bulk formulations, is
utili~ed as an additional solvent useful in the bulk formulations. It is
mlscible with alkanols and is a superior organic solvent for the picric acid.
d) Tertiary long chain amines. The action of the amine is as a particu-
late reducer and a preferred compound is Primene 81R which is tertiary dodecyl
amine.
e) Water. As to the water additive, a purified water free of extraneous
metal ions is preferred, although tap water is operable.
The introduction of the composition into a diesel or gasoline bulk
con~ainer is made in a facile manner by pre-measurement and adding the composi-
tion based upon the number o~ gallons in the container. Such bulk addition
may be made per United States gallon by utilizing a ratio of 1:1,000 to
1:2,000 dosage addition by volume with a preferred dosage of 1:1600
For atomized use, a preferred modus is to introduce a mixture of
alcohol and active ingredients into the motor utilizing a system such as the
Harlo MotorKlean Fuel System (manufactured by Harlo Repower Ltd., Clearbrook,
B.C., Canada) for direct injection into the line leading into the manifold.
A preferred solvent utilized in the Harlo equipment or the injection is ~by
1~ volume):
25 % Isopropyl alcohol
25 ~ Water
12.5 % Ethanol
12.5 % MSX Mix
25 % Methanol
The introduction of the MSX Mix into the combustion chamber when
using the water-alcohol mixture in the "Harlo Device" further enhances the
operation. This results from being able to actually control the amount of
catalytic material being introduced. By a very carefully selected orifice,
one milliliter of the atomized mixture is introduced for every mile traveled.
In this way, at no time is a heavy concentration of the "fuel saver" or
"energy extender" introduced into the combustion chamber to be wasted. By
the very makeup of the compound and its volatility, it is introduced in the
sable vapor phase.
As a result of utilization of the present composition, it has been
found by tests that improvements in fuel economy between 12.5 and 15.5 percent
urban and up to 27 percent highway conditions have been experienced. The
variable range is due to make, condition, size of the vehicle, coupled with
the variations in road conditions that drivers have at city versus highway
driving, etc. It can be further stated that a mean average mileage improvement
i8
for all tests is about 20 %. Based currently on the United States price per
gallon of about 70 cents per gallon, this means that about 14 cents on every
gallon of gasoline can be effec~ed in savings.
The present invention also has use for domestic heating and light
industrial oils (#2 and #3) used in furnaces and boilers. Her the same
catalytic action of the ferrous ion takes place and more complete combustion
is the result, Less carbon and residue is formed and the heat is not insulat-
ed from the transfer equipment. A greater calorific value (in BTU's) is re-
lcasc~, giVillg more heat and energy for the same given amount of fuelO This~
l~ o course, results in less and more acceptable emissions from the chimney or
stack.
In the case of bunker fuels ~#6), these fuels are heavier and much
more viscous compounds, often containing considerable amounts of organic or
inorganic salts, which upon burning can diffuse and cause heavy melts or ashO
Stated otherwise, when used with residual fuels ~#~ #5) where high
temperature, slagging, or corrosion may be the main problem, the present addi-
tive Ina~ be used in order to serve as a combustion catalyst to further improve
the burning properties of the fuel proper; i.e., to improve the C02 content of
the flue gas and reduce the amount of the organic or carbonaceous material
~n tllat would be left bchind.
With respect to jet engines and jet fuels, which are lighter, and
aviation-type fuels or with napthas and special distillates for gas turbines,
~he adcl:itive combinations will reduce coke and varnish deposits in the engines
and e.~haust parts.
EXAMPLE 1
MSX Mix Formulation
Toluene and isopropyl alcohol were mixed together. The trinitro-
phenol ~picric acid) was introduced to this mixture and stirred gently. It
dissolved completely when left overnight. The nitrobenzene was added with a
slight stir. The ferrous sulfate was dissolved in a small amount of hot water
6~ 6l~3
~a maximum of one-half gallon for one hundred gallon mix) and added to the
mixture.
The product was allowed to stand overnight. It was inspected for
any sediment settling, after Quality Control Tests were made and the product
passed. It was released for ultimate packaging.
The ~ater usually present Nith the trinitrophenol (picric acid) was
taken into consideration in the formulation of this product.
EXAMPLE 2
Exhaust Emission Test with MSX Mix
In May 1977 at the testing site of Scott Environmental Technology,
lnc., two series of tests were run according to the 1975 Cold Start Exhaust
Emission Test with the obj ective to determine the effectiveness of the MSX
~uel additive when mixed directly in bulk with in-tank gasoline in reducing
exhaust emissions and improving fuel economy. The site of the test was Scott's
Plumstedville, Pennsylvania, facility, which is certified by the United States
Environmental Protection Agency for conducting the federal exhaust 0mission
test herein described.
Test Vehicle Description
. ~9 Both emission tests were performed on a 1976 Chevrolet Impala sedan
(vin: lL57H5113039) equipped with a standard 350 cid, V-8 engine with 2-bblo
carburetor and automatic transmission. The vehicle was received in stock
condition for the first emission test3 with a pretest mileage of 23,605.7.
The vehicle was equipped with the stock 1976 Chevrolet emission control equip-
ment, including catalytic converker.
Basic Test Data
The additive (Natural Resources Guardianship International, Inc.3
l~est Orange, New Jersey) consisted of a gasoline fuel additive (MSX Mix) mixed
directly in the gasoline fuel tank of the test vehicle. This mixture consisted
of one part additive to 1600 parts gasoline with ~he following composition
denoted 5/77:
~7~8
Ferrous sulfate .16 g
Picric acid ~trinitrophenol) 2.8 g
Toluene 2.7 kg
Isopropyl alcohol .9 kg
Nitroben~ene .13 g
Water Balanc0
: For bo~h tests, the baseline fuel used was Texaco's "lead-free" gasoline.
Test Procedure Description
The t~io ~975 cold start emission tests were performed in accordance
~ith Federal Register Volume 41, Number 146. Deviations from this procedure
included use of Natural Resources Guardianship International's in-~ank fuel
supply for both the baseline and device tests, and the calculation of carbon
dioxide mass emissions for use in determining fuel economy.
The test vehicle was delivered to Scott's Plumsteadville, Pen syl-
vania, facility by 1600 hours on May 3, 1977, with the initial "cold soak"
beginning by 1700 hours. The following morning the dynamometer was warmed up
with a non-test vehicle and the load set at 14.7 RHP at 50 miles per hour (the
vehicle was equipped with factory air conditioning). The dynamometer inertia
was fixed at 5,000 pounds. The baseline emission test (stock conditionj no
device) was begun at 1032 hours and completed by 1112 hours.
Following the baseline test, several additional emission tests were
per~ormed on the test vehicle including one 1975 Federal Cold Start Test
~Scott Reports SET 1620-01-0577 and SET 1620-02-0577) and several 1972 "Hot-
Start" emission tests ~Scott Report SET 1620-03-0577).
On May 16 and 17, 1977, Scott personnel blended in-tank fuel (1 part
~SX Mix additive to 1600 parts Texaco lead-free gasoline) then accumulated
500.7 miles on the vehicle. (Mileage start: 25871.8; mileage end: 26372.5).
The "cold soak" period began at 1715 on May 17, 1977, and was terminated at
the beginning of the 1975 "Cold-start" lest No. 3 at 0927 hours on May 18.
The basic equation used to calculate the fuel economy of a vehicle,
~7~
in miles per gallon, from the mass emission data gathered during a 1975 Federal
Emission Test is as follows:
m _ grams of carbon/gallon of fuel
Pg grams of carbon in exhaust/mlle
Summary of Results
.
The data presented in Table l below summarizes the vehicle exhaust
emission and fuel economy tests performed. The exhaust emissions are presented
in grams per mile for total hydrocarbons, carbon monoxide and oxides of nitro-
gen. Fuel economy measurements are shown in miles per gallon. Also included
are the applicable 1976 Federal Exhaust Emission Standards for light duty
l~ vehicles.
In comparing the two sets of test results, use of the MSX Mix addi-
tive mixed with the in-tank fuel reduced carbon monoxide and hydrocarbons
while increasing oxides of nitrogen emissions. In addition, fuel economy im-
proved from S.72 MPG to 10.65 MPG.
- 10 -
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EXAMPLE 3
-- -
In the same manner as the procedure utilized in Example 2, another
series of tes~s utilized the MSX additive designated 7/77. This additive had
the composition per United States gallon as follows:
Ferrous sulfate 1.36 grams
Picric acid 45.36 grams
Toluene 2.38 kg
Isopropyl alcohol 1.02 kg
Nitrobenzene 2.72 grams
Long chain amine; e.g.,
tertiary dodecylamine 1.66 grams
Water Balance
and the follo~Ying results were obtained as shown in Table 2.
- 12 -
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- 13 -
-EXAMPLE q
An ASTM D-13-56 Copper Strip and Stainless Steel Corrosion Test was
effected using the 7/77 additive formulation (see Example 3) comparing various
inorganic metal salts with ferrous sulfate. This test was made for 3 hours
at 212F.
Salt ASlM D-13-56 Results
Ferrous sulate No. 1 ~pass) ~No change)
Nickel sulfate No. 2 (Dark tarnish, multicolored, peacock)
Nickel nitrate No. 3 ~Magenta, light gray)
Cadmium sulfate No. 3 ~Magenta, brown)
A vapor phase corrosion test was made where vapors were utilized for 30 minutes
at 300 to 500F. In this case the iron salt showed slight discoloration
whereas the other metal salts blackened with slight pitting. Both stainless
steel and copper strips were used in this test.
- 14 -
