CA1107068A

CA1107068A - Picric acid (trinitrophenol) with ferrous sulfate as fuel additive

Info

Publication number: CA1107068A
Application number: CA300,176A
Authority: CA
Inventors: Harry M. Webb
Original assignee: Natural Resources Guardianship International Inc
Current assignee: Natural Resources Guardianship International Inc
Priority date: 1977-04-01
Filing date: 1978-03-31
Publication date: 1981-08-18
Also published as: DE2812265A1; ES468449A1; SE7803656L; JPS5735754B2; IT7821939A0; AR219318A1; NO781146L; FR2385791A1; IL54368A; IT1094312B; FR2385791B1; GB1574297A; ATA219878A; JPS53134003A; NL7803449A; IL54368A0; DK145378A; BR7802037A; GR64144B; AT365628B

Abstract

Abstract of the Disclosure The present invention relates to an energy-saving fuel additive suitable for jet, gasoline and diesel engines and also suitable for addition to domestic heating and light industrial oils (#2 and #3) and residual or bunker fuel (#4, 5, and 6). The fuel additive comprises as active ingredients a catalytic mixture of a major proportion of picric acid and a minor proportion of ferrous sulfate. This additive may be utilized in bulk by addition of a concentrate mix to a tank or fuel container.

Description

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:

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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.

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.

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.

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.

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~_ 4 -- -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.

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-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.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A fuel additive suitable for internal combustion, jet and diesel engines consisting of an active ingredient formulation comprising a mixture of picric acid and ferrous sulfate in a mixed solvent of lower alcohol, toluene, and water, the picric acid being present in an excess by weight over the ferrous sulfate.

2. The additive according to claim 1 wherein the additive is in atom-ized form for introduction into the engine.

3. The additive according to claim 1 which additionally contains a minor amount of nitrobenzene as a solvent.

4. The additive according to claim 1 which additionally contains a minor amount of tertiary dodecylamine as a particulate reducer.

5. A fuel additive suitable for direct bulk addition to gasoline and diesel fuel containers which comprises in one United States gallon:
Ferrous sulfate .08 - 1.4 g Picric acid (trinitrophenol) 2.8 - 45.0 g Toluene 2.4 - 1.0 kg Isopropyl alcohol 1.0 - 2.4 kg Nitrobenzene .08 - 2.7 g Long chain amine .2 - 1.7 g Water Balance

6. The additive according to claim 5 wherein the preferred amount in one United States gallon is:
Ferrous sulfate 1.4 g Picric acid (trinitrophenol) 45.0 g Toluene 2.4 kg Isopropyl alcohol 1.0 kg Nitrobenzene 2.7 g Long chain amine 1.7 g Water Balance

7. The additive according to claim 1 wherein the dosage utilized for addition to fuel is 1:1,000 to 1:2,000 additive to fuel.

8. The additive according to claim 1 wherein the dosage utilized for addition to fuel is about 1:1,600 additive to fuel.

9. A method for treating fuels for gasoline and diesel engines which comprises adding thereto to each United States gallon an additive/fuel com-prising a mixture of picric acid and ferrous sulfate in a mixed solvent of lower alkanol, toluene, and water in a dosage of about 1:1,000 to 1:2,000 additive to fuel, the picric acid being present in an excess by weight over the ferrous sulfate.

10. The method according to claim 9 wherein the dosage is about 1:6,000 additive to fuel.

11. The method according to claim 9 wherein the additive is in atomized form for introduction into the engine.

12. The method according to claim 9 wherein the additive additionally contains a minor amount of nitrobenzene as a solvent.

13. The method according to claim 9 wherein the additive additionally contins a minor amount of tertiary dodecylamine as a solvent.

14. A fuel additive suitable for use in bunker and residual fuels which has the following ingredients per United States gallon:
Ferrous sulfate 4 - 5.6 g Picric Acid (trinitrophenol) 8 - 12 g Toluene 4 - 5.6 kg Isopropanol .8 - 1.2 kg Long chain amine .2 - 1.7 g Water Balance

15. The additive according to claim 14 wherein the ingredients have preferred values per United States gallon as follows:
Ferrous sulfate 4 g Picric Acid ~trinitrophenol) 8 g Toluene 4 kg Isopropanol .8 kg Long chain amine .2 g Water Balance

16. The additive according to claim 14 wherein the dosage is in the ratio of 1:1,000 to 1:2,000 additive to fuel.

17. The additive according to claim 14 wherein the dosage is in the ratio of about 1:1,600 additive to fuel.

18. A fuel additive consisting of an active ingredient formulation com-prising 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.

19. A fuel additive according to claim 5 or 6 wherein the long chain amine is tertiary dodecylamine.

20. A fuel additive according to claim 14 or 15 wherein the long chain amine is tertiary dodecylamine.

21. A method for treating fuels which comprises adding thereto to 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 1:1,000 to 1:2,000 additive to fuel, the picric acid being present in an excess by weight over the ferrous sulfate.