US3341310A - Fuels for internal combustion engines - Google Patents

Description

United States Patent 3,341,310 FUELS FOR INTERNAL COMBUSTION ENGINES Ernst Drouven, Verona, Italy, assignor to Torrimetal Trust, Vaduz, Liechtenstein No Drawing. Filed Apr. 15, 1963, Ser. No. 272,880 Claims priority, application Austria, Sept. 26, 1958, A 6,768/58 14 Claims. (Cl. 44--69) This application is a continuation-in-part of my copending application Ser. No. 842,228, now abandoned, filed Sept. 25, 1959, for Motor Fuels) The present invention relates to improved fuels for internal combustion engines, and more particularly to a metal-containing motor fuel which, due to its content of particular metals, in particular form, and at particular concentrations, has improved characteristics and increases the performance of gasoline (spark ignition) or diesel (compression ignition) engines operated therewith.

In the present specification and in the appended claims, the term motor fuel is used to designate all liquid hydrocarbon fuels suitable for use in internal combustion engines of all type, including gasoline, kerosene, and diesel fuel. Such fuels are composed of a mixture of various types of hydrocarbons boiling within the range of about 80 to about 800 F.

It has been proposed to improve the performance of internal combustion engine fuels by incorporating simultaneously therein lead, copper and Zinc salts. In internal combustion engines operated with such fuel compositions, deposits are formed on the cooled cylinder walls, said deposits acting as a seal between the cylinder wall and the piston, and thus increasing the compression pressure.

It has been found that the deposits in the engine caused by motor fuels of this type have a substantially different effect, depending on the quantities of zinc, copper and lead compounds added to the fuel, depending on the type of such compounds, and also depending on the proportion of the lead relative to the'zinc and copper. Furthermore, it has been found that extraordinary effects, especially in view of the sealing film between the cooled walls and the piston resulting from combustion residues, are produced by additionally incorporating into the fuel halogenated compounds which react in the combustion chamber with the metals to form metal halogenides.

It is accordingly a primary object of the present inven tion to provide a fuel for internal combustion engines which has the optimum advantages obtainable by the named metals, especially as to the sealing effect of the film deposited on the cooled walls produced during the combustion of the motor fuel containing the additives in accordance with this invention.

Another object of this invention is to provide a fuel whose deposits in the engine improve anti-knock properties.

A further object of this invention is to provide gasolines and diesels fuels of improved combustion characteristics.

A still further object of this invention is to provide a process of making improved motor fuels by the addition of a special composition containing zinc, copper and lead compounds in certain amounts and proportions.

As yet another object, the present invention provides for the preparation of concentrated solutions of the additive to be incorporated into the fuel.

In the preparation of copper, zinc and lead compoundcontaining motor fuels, difficulties were encountered due to the fact that the simultaneous solubility of lead, copper and zinc salts in the commonly used gasolines and diesel fuels is rather poor. It was therefore diflicult to provide the required concentrations of the metal additives for the fuel. It is of importance that the mentioned metals must be used in the form of salts which are compatible with one another with respect to their solubility, and furthermore that in and together with the motor fuel the salts should be present in the form of a truly stable solution. For the production of the motor fuel in accordance with the present invention it is furthermore of great importance that the added metal compounds are not only soluble in the concentrations intended to be present in the motor fuel, but also in considerably higher concentrations.

The use of copper, zinc, and lead salts would be extremely limited if, due to an insufficient solubility of the individual compounds, the total commercial motor fuel would have to be mixed with large amounts of various weakly concentrated solutions in excessively large stirring devices. The desired additive solutions which can be added in rela tively small volumes to the motor fuel can only be produced by using compounds of good solubility. Accordingly, it is necessary in order to achieve the objects of the present invention to use the metals copper, zinc and lead in the form of the naphthenates of these metals.

It is accordingly still a further object of the present invention to provide concentrates of the metal salts of the present invention which can easily be added to any motor fuel without requiring special mixing devices, and which, when added to such motor fuels, will directly result in improved performance thereof.

With the above and other objects in view, the present invention mainly comprises the provision of a motor fuel comprising per each liter of fuel about 0.5-15 mg. of zinc in the form of zinc naphthenate, about 0.5-25 mg. of copper in the form of copper napht-henate, and lead in the form of lead naphthenate in an amount at least about 2 times the weight of the sum of the zinc and copper content, the total amount of zinc, copper and lead being between about 3 and 200 mg. per liter of fuel.

It has also been found necessary in accordance with the present invention to provide in the composition, in addition to the above mentioned metals, a brominated and/or chlorinated hydrocarbon in an amount such as to obtain a 10% to preferably 35% to 50% bromination of the added metals in the case of brominated hydrocarbons, and a 20% to 200%, preferably 70% to 100% chlorination of the added metals in the case of the chlori nated hydrocarbons. The terms bromin-ation and chlorination are used herein to designate the conversion of the added metals into their maximum valency halogen compounds. If brominated and chlorinated hydrocarbons are used concurrently, they should be added in such proportions as to provide the amounts of bromine and chlorine required for the above stated halogenation levels.

In order to achieve the optimum halogenation effect it is most preferred to use brominated benzene, brominated ethylene, chlorinated benzene or chlorinated ethylene as the halogenated hydrocarbons. Thus, bromo benzene, ethylene dibromide, ohloro benzene and/or ethylene dichloride will give the most desirable results.

The additive composition of the present invention which contains 05-15 mg. of zinc in the form of zinc naphthenate, about 05-25 mg. of copper in the form of copper naphthenate, and lead in at least double the amount of the total of the zinc and copper, the total amount of the zinc, copper and lead being greater than 3 mg., and being as high as a total of 200 mg., are suitable not only for gasoline for internal combustion engines, but for diesel oils and for fuels in general for all types of internal combustion engines.

A preferred motor fuel in accordance with the present invention comprises per each liter of hydrocarbon fuel about 3.5-8 mg., most preferably about 7.2 mg., of zinc in the form of zinc naphthenate, about 0.55 mg.,

most preferably about 3.4 mg, of copper in the form of copper naphthenate, and lead in the form of lead naph- 4 gasolines containing 3 cc. of lead tetraethyl and the additives of the present invention):

Composition of the additives with reference to the metals (mg/l.)

Composition of the residues, without oxygen, sulfate and halogen (percent) thenate in an amount of about 2.5-3 times the weight of the sum of the Zinc and copper content, most preferably about 29.4 mg. of lead; and in addition a brominated and/ or chlorinated hydrocarbon of the type mentioned above, in an amount sufiicient for an approximately 35-50% bromination or an approximately 70100'% chlorination of the metals present.

As pointed out above, the composition of the present invention has the efiect of forming a film between the cylinder walls and the piston which improves the compression and reduces the friction between the cylinder and piston, thus improving the entire operation of the engine and rendering the operation of the same much more economical.

While the present invention is not meant to be limited as to any theory of how the film formation takes place, the following theory is given in the hope that it will help others to better understand the invention. In any event the fact is that the film mentioned above does form.

It was proved analytically that during the combustion halogenides and sulfates, as well as oxides are formed. While a portion of the salts and oxides are expelled with the exhaust gas, another portion precipitates on the cooled cylinder wall. This deposit forms a film of a certain thickness, which by the movement of the piston is constantly being damaged, that is by being pushed forward. On the freed parts of the cooled wall new precipitation is deposited so that the film is constantly being formed partially destroyed and regenerated.

If the engine is opened there is found between the piston head and the motor block a porous sealing ring which is level at the top, that is pressed flat and which is about 1-2 mm. (depending on the size of the engine) wide, is conical towards the bottom and which fills the space between the piston head and the motor block in a wedgeshaped manner.

This ring can be taken off and upon analysis is found to have essentially always the same composition. Lead as lead chloride and/or lead bromide, and as lead sulfate, forms the basis of the film, while copper and Zinc compounds quantitatively constitute only a small portion of the deposits. The presence of these metals is, however, of critical importance for the formation of the film, and their amount is likewise decisive for the formation and the efficiency of the film in accordance with the present invention. Thus, for example, it has been found that the copper content influences the combustion and thereby the amount and proportion of C and H in the deposits. The content of C and H in the deposits in order to achieve the most desirable effects has been found to be about 30- 35%, whereby the ratio of C:H is about 1:1.

It has been found that by using the composition of the present invention within the ranges set forth these results are achieved.

Using gasolines with the additives of the present invention it has been found that varied compositions of the additive with reference to the naphthenates, to a certain degree independently of the used fuel, give the following combustion residues (the following analyses were made on residues from motor fuels which were formed with It may thus be seen that the amounts of metal additives used in accordance with the present invention are critical for the achievement of the desired effects.

It has been found that the addition of less than about 0.5 mg. of zinc, about 0.5 mg. of copper, and less than about 2 mg. of lead does not produce any effect at all, or precisely, does not result in the improvements obtainable in accordance with the present invention. On the other hand, if the zinc content of the fuel is too high, undesirable and even harmful deposits are formed in the combustion chamber. Furthermore, gasolines containing too high an amount of zinc tend to knock. Too high an amount of copper does not result in undesirable deposits in the combustion chamber, but causes an excessive increase in the compression pressure due to the formation of a seal which prevents the necessary lubrication by an oil film on the cylinder wall.

The necessity of a large amount of lead is also shown by the above analyses of the combustion deposits.

The additives of the present invention may be added not only to unleaded fuels, but also to leaded motor fuels, that is fuels containing soluble lead compounds, particularly lead tetraethyl, as anti-knock agents. It is common practice to use in conjunction with lead tetraethyl certain halogenated hydrocarbons as scavenging agents. In the normal leaded motor fuel the contents of lead tetraethyl and halogenated hydrocarbons are balanced in such Way that in the combustion chamber theoretically the total amount of lead becomes volatile as lead-bromide or lead chloride, and is expelled with the exhaust gases.

In order to obtain a complete reaction between the lead and the halogen of the added halogenated hydrocarbon it has been suggested that the halogenated hydrocarbon be present in an excess. Thus, for example, the following two preparations are available on the petroleum market under the name of Ethyl fluid:

1 T-Fluid or Aviation-Octyl for airplanes Motor-Mix or Motor'O ctyl for automobiles Despite the excess of halogenated hydrocarbon experience has taught that on running the engine with the leaded gasoline a residue of lead oxide precipitates on the piston head, which means that the desired reaction was not complete because of the incomplete reaction of the lead with the halogenated hydrocarbons.

The combustion residues which are formed from normal lead-containing gasoline and which are deposited at the piston heads and the motor head reduce the size of the combustion chamber and thus increase the compression undesirably. However, it is impossible to observe an in- 'about 350 F. and about 800 crease in the sealing which should be determined by the reduction of the quantity of the amount of gas blown through. On the contrary, the undesirable incrustation causes a gumming up of the piston rings, the latter becoming stuck, and thereby reducing the sealing. Thus, residues of ordinary lead-containing gasoline cannot be compared with the sealing film and with the ring formation of the piston head which is achieved with the additive composition of the present invention, which leaves the piston rings freely mobile and which increases the compression simultaneously reducing the incrustation and the amounts of gas blown through.

Although by the use of an excess of the halogenated ydrocarbon and even in cases of complete reactions of the lead with the halogenated hydrocarbon which is present in a large amount, it has been found preferable in the case of moderately leaded gasoline not to change the above indicated amount of chlorine and/ or bromine hydrocarbon. Only in the case of very strongly leaded gasoline can the addition of halogenated hydrocarbon be omitted. The omission is possible in the case of an addition of at least 0.3 cc. of lead tetraethyl per liter and can unconditionally be recommended in the case of 0.6 cc. of lead tetraethyl per liter.

In the case of heavily leaded gasolines an amount of lead remains available for the formation of the desired film. It has thus been determined that with an addition of at least 0.3 cc. of lead tetraethyl and more, it is sufficient if instead of double the amount of lead, with respect to the amount of copper and zinc, that the amount of added lead be 80-100% of the total amount of the copper and zinc.

In the examples given below the effects of the additives according to the present invention are shown, when adjusted with respect to leaded gasoline.

Gasoline as used in connection with the present invention is a well known article of commerce for use in internal combustion engines operating on the Otto cycle. It is composed of a mixture of various types of hydrocarbons, including aromatics, olefins, parafims, isoparafiins and naphthenes. These mixtures are obtained from petroleum by refining processes including fractional distillation, catalytic cracking, hydroforming, alkylation and extraction. Motor gasoline boils between 80 F. (initial boiling point) and about 450 .F., when tested by A.S.T.M. method 86. Its vapor pressure by A.S.T.M. method D323 varies for use at different seasons between 7 and 15 lbs. per square inch at 100 F.

Among the diesel fuels used in the practice of the present invention are all of the commonly sold grades including kerosene. Kerosenes normally have boiling ranges between 100 F. and about 600 F. and are sometimes referred to in the petroleum industry as No. 1 fuel oils. Diesel. fuels in general have boiling ranges between F. and are described more fully in A.S.T.M. specification D-975-53T as amended.

Such fuels are derived from petroleum crude oils by a variety of processing operations which may include atmospheric and vacuum distillation, catalytic and thermal cracking, catalytic and thermal reforming, visbreaking, hydrotreating and the like. Like gasolone, diesel fuel is composed of a mixture of various types of hydrocarbons including parafiins, isoparafiins, naphthenes and aromatics.

In the case of the production of motor fuels in accordance with the present invention, where the motor fuel contains more than 1% sulfur, the efliciency in accordance with the present invention can be impaired through acids of the sulfur formed during combustion, Which partly bind amounts of metals added. In such cases, the amounts of metals added in accordance with the present invention should be increased according to the content of sulfur, e.g. the content of sulfur of 2%, the

amounts of the metals (zinc, copper and lead) should be doubled.

The following examples are given to further illustrate the present invention. However, the scope of the invention is not meant to be limited to the specific details of the examples.

The following examples were carried out with naphthenates of copper, lead and zinc. For the preparation of the required master solutions, commercial naphthemates of lead, copper and zinc made by Hoechster Farbwerke, Frankfurt-am-Main, were used. These naphthenates were individually dissolved in a gasoline having a boiling range of 100 C. in such amount as to obtain (1) a lead solution containing 58.8 g. of lead per liter, (2) a copper solution containing 13.6 g. of copper per liter, and (3) a zinc soluton containing 28.8 g. of zinc per liter.

EXAMPLE 1 50 cc. of the lead solution, 25 cc. of the copper solution and 25 cc. of the zinc solution were mixed with 3.0 cc. of mono bromo benzene and the resulting solution was mixed with liters of commercial unleaded gasoline (DEA=Deut-che Erdol A.G., Hamburg, Production 1955/56). The gasoline contained 29.4 mg. of lead, 3.4 mg. of copper, 7.2 mg. of zinc and 0.03 cc. of mono bromo benzene per liter.

Bench test experiments with 9. Fiat 1100 engine operated on this fuel showed, after running the engine for 20 hours at 2500-3000 r.p.m., a maximum performance of 31 H.P. in contrast to 30 H.P. observed when the engine was operated on the same gasoline not containing the additives of this invention. Furthermore, there was found a decrease in the fuel consumption from 246 g./H.P./h. to 231 g./H.P./h. at 2500 rpm. At other r.p.m. values, similar savings in fuel consumption could be obtained.

The amount of gas blown through into the crankcase was substantially reduced and stabilized at a minimum, which was measured and found to be 50% of the amount of gas blown through and measured when the same motor was operated without the additive of the present invention. The amount of gas blown through with standard gasoline was measured to be 88 cc. per second at 3000 r.p.m. and 11.6 H.P. output, and this blown through amount dropped for the same number of revolutions and the same output to 44 cc. when the gasoline with the additive of the present invention was used. At 2500 r.p.m. and 6.7 H.P. the amount of gas blown through dropped from 60 cc. to 30 cc.

The increase of the output or efiiciency corresponded to the improved sealing effect obtained according to the present invention and to a corresponding increase of the compression pressure with a simultaneous improvement of the combustion. In the exhaust gases a drop of the CO percentage and an increase of the CO percentage was found. Irrespective of the increased compression pressure, no tendency to knock could be determined or found.

EXAMPLE 2 25 cc. of the lead solution, 12.5 cc. of the copper solution, and 12.5 cc. of the zinc solution were mixed with 0.935 cc. of ethylene dibromide and the mixture was added to 50 litres of the gasoline of Example 1. The additives thus contained with respect to the metal contents the same composition as in Example 1. However, the ha1ogenof 0.0187 cc. of ethylene dibromide instead of 0.03 cc. liter.

Bench test experiments with this fuel were carried out with the same Fiat 1100 engine as in Example 1. After the test described in Example 1 the engine was operated on the fuel containing the above additives for 1 hour. The maximum performance remained at 31 H.P. as in Example 1, with the tendency however, to be slightly greater. The fuel consumpton at 2500 revolutions per minute fell from 231 g./H.P./h. to 213 g./H.P./h..A similar decrease was observed at other r.p.m. values.

of mono bromo benzene per The composition of the exhaust gases was about the same as in Example 1. The same applies to the gas pressure in the crankcase and to the compression pressure. Likewise, no tendency of the engine to knock was found.

EXAMPLE 3 The additive mixture described in Example 1 was added to 100 liters of commercial diesel fuel of the following characteristics:

The diesel oil had a specific weight of 0.840 and a sulfur content of 0.96%.

Using this fuel tests were carried out in a 1953 Borgward diesel passenger car (1800). After a relatively short driving time (distance covered 50 km.) a marked improvement in engine performance manifested itself in a considerable increase of the accelerating power and also a better climbing power in mountainous terrain. When go ing up hills, the increase in engine performance always made it possible to use a higher gear than previously.

After driving the car over a distance of 30,000 km. the engine was opened up and no residues were found. The increased performance and the decreased fuel consumption remained at the same good levels after driving the car for an additional 20,000 km.

EXAMPLE 4 An additive was added to 50 liters of the same diesel oil as in Example 3 so that the composition with respect to the metals was the same as in Example 3. However, the addition of the halogenated hydrocarbon amounted to 0.045 cc. and in another case to 0.06 cc. of mono bromo benzene per liter.

Road tests were conducted with the same Borgward diesel car as used in Example 3. The increase in engine performance rose to twice the amount observed in the test of Example 3. This was apparently due to the increase of the halogen addition by 50% and by 100% respectively. The increased efliciency was particularly observable in connection with the increase of accelerating power and thereby covercoming the characteristic sluggishness of diesel engines.

EXAMPLE 5 The following test was carried outwith unleaded ARAL Super gasoline to which per liter of fuel were added 29.4 mg. lead, 0.6 mg. copper and 3.6 mg. zinc, and furthermore 0.006 cc. ethylene dibromide and 0.011 cc. ethylene dichloride, whereby corresponding amounts of the above described master solutions of the respective metals were used.

Using this gasoline tests were carried out with a Topolino (Fiat 500A) motor car, model year 1948. This car was run 200,000 km. with the gasoline containing the additive described above, according to the invention. The engine was over-hauled only once after having been run 119,000 km.

After 200,000 km. the car was run with normal gasoline, that means with gasoline without the respective additive, and it was observed, that the motor performance decreased progressively. Finally the motor could move the car only on a level road at a maximum speed of 55 km./ h. Already at a 2% inclination it was necessary to change into second gear. After running in this way the gasoline with the additive of the present invention was used again and surprisingly it was found that after travelling for only a few kilometers the motor regained. progressively its former performance.

The care would take any inclination of up to 5% in highest gear and the maximum speed on level terrain was increased to 90 km. per hour. This performance remained the same with the gasoline containing the additive according to the present invention upon further running with the same motor. This effect is therefore clearly based on the use of the gasoline with the additive of the present 5 invention.

EXAMPLE 6 16 cc. of the lead solution, 25 cc. of the copper solution and 25 cc. of the zinc solution were added to 100 liters of commercial gasoline which had been leaded with 10 0.3 cc. per liter of lead tetraethyl. The gasoline has the following characteristics: Specific wt. at C. 0.726 Initial boiling 32 15 Boiling until 55 percent 14.5 Boiling until 70 do.. 31 Boiling until 100 do 55 End of boiling 192 Olefin content percent 21 Aromatic content do 15 Each liter of the gasoline thus contained 9.4 mg. of lead, 3.4 mg. of copper and 7.2 mg. of zinc.

Using this fuel test drives with a Leoncino bus (spark plug engine of 2.545 liters capacity) produced by the O.M.-Works Brescia (Italian Fiat group) were taken. The bus carried a load of 5000 kg. The test distance amounted to 201 km. and was covered nine times at the same average speed of 52.5 km. per hour.

The first drive was taken with a regular gasoline not containing the additives of this invention. The fuel consumption amounted to 25.746 liter/100 km. The following eight drives were taken with the above described gasoline according to this invention and gave the following results:

Fuel consumption in liters Total Per 100 km.

2d Drive (1st; Drive was taken without additives) 48. 300 24. 029 (1 Drive 920 22. 845 43. 900 21. 840 44. 630 22. 203 43. 310 21. 547 40. 000 19. 900 38. 880 I9. 343 38.300 19. 054

As may be seen from these data, the fuel consumption decreased by 25.99% after going a total distance of 1608 km. as compared with the fuel consumption observed when operating the bus on a regular fuel without thev additives of this invention.

EXAMPLE 7 A gasoline containing 0.45 cc. per liter of lead tetraethyl and having the following characteristics:

Specific wt. at 15 C. 0.731 Distillation range, C. 35-196 Content of olefins percent 21 Content of aromatics do 12 was mixed with 0.6 mg. of copper, 7.2 mg. of zinc and 6.2 mg. of lead per liter, all three metals being in the form of their naphthenates.

This was achieved by taking from the master solutions 105.5 cc. of the lead solution, 44.1 cc. of the copper solution and 250 cc. of the zinc solution, mixing the solutions with each other, and then adding the resulting mixture to 1000 liters of the gasoline.

Using the gasoline containing the additives tests were carried out with a Fiat motor 1100-103 which had been run 50,975 km. with normal gasoline. In a first test series the motor was run in worn condition, and in a second series after a general overhaul. In both cases measurements were taken with full load and partial load.

75 The following tables give the percentage difference came soft and easily removable. On the motor head there was practically no residue and the piston rings were free of residue and freely movable.

EXAMPLE 8 8 cc. of the lead solution, 12.5 cc. of the copper solution and 12.5 cc. of the zinc solution were mixed with 100 liters of a commercial leaded super gasoline con- Table I [Percentage changes of measurements indicating the engine performance when using gasoline containing the additive of the present invention as compared to the use of normal gasoline] Measurements at full load Revolutions Before the overhaul After the overhaul per minute Performance, Specific Amount of gas Specific Amount of gas Horsepower percent consumption, blown Horsepower Performance consumption, blown percent through, percent through, percent percent Table 11 Measurements with partial load Revolutions per Before the overhaul After the overhaul minute Performance, Specific consump- Amount of gas Specific consump- Amount of gas Horsepower percent tion, percent blown through, Horsepower tion, percent blown through,

percent percent Table III taining 0.6 cc. of lead tetraethyl per liter, and having WITH NORMAL GASOLINE the following characteristics;

' 0 Specific Amount MW 50 pwfi W a 15 C w- 0.739 Tests Revolutions consumption, blowri1 Olefin C t nt percent 14.2 permlnut gJ J gag Boiling range 32197 For mass testing purposes the gasoline containin the Full load with worn 4,000 268 400 g engim 3,000 273 292 additives was utilized in the vehicles of a large industrial Partimoad after 3 500 247 132 enterprise which owned passenger cars and trucks, and overhauL 2:000 334 62 whose total consumption of the gasoline was three million liters. WITH GASOLINE CONTAINING THE DD E Based On spot examinations there was found to be a reduction in gasoline consumption amounting to Full load with Worn 4, 000 259 280 14.78%. The reduction in gasoline consumption was more englne. 3,000 266 142 pronounced in trucks than in passenger vehicles and Partial load after 3, 500 232 70 varied, depending on the diiferent types of engines, beoverhaul. 2,000 300 36 tween 7 and 20%. In general an increase in the accelera- With respect to the appearance of the motor before and after the use of the gasoline containing the additive of the present invention the following should be noted. The used motor exhibited before application of the invention an incrustation of approximately 1.5 mm. on the piston head and on the motor head. This incrustation was black and hard, that is a typical oil crust. The residue was left in the engine when the gasoline with additives was introduced into the engine. After the test with the gasoline containing the additive the incrustation on the piston head was reduced to about 0.2 min; it be- EXAMPLE 9 17.5 cc. of the lead solution, 4.5 cc. of the copper solution and 12.5 cc. of the zinc solution, 0.3 cc. ethylene dibromide and 0.6 cc. ethylene dichloride were added to of one of the common Volume percent Content of olefins 3 Content of aromatics 30:9 Content of paraifins and naphthenes 66.0 Content of sulfur 0.034

To the leaded commercial gasoline therefore per liter were added 10 mg. lead, 0.6 mg. copper, 3.6 mg. zinc, 0.003 cc. ethylene dibromide and 0.006 cc. ethylene dichloride.

The following bench tests were carried out with this gasoline using a Daimler-Benz motor M121, Mercedes engine type 180b. The motor was a factory new motor and tuned mechanically so as to be in the best possible condition. This motor was run before the test for 100 hours on the test bench thus reaching its mechanical peak condition and excluding also any improvement in the performance by mechanical means. Having recorded the performance diagram and amounts of gases blown through without the use of the additive, the engine was then run for 36 hours on the bench with gasoline containing the invention additives, in order to build up the metal salt film. After that the performance diagram and the amount of gas blown through were recorded, relating to the use of the additive.

Running the engine on gasoline with additive it was found that with the same amount of engine fuel a longer running time according to the prescribed test program was made possible, amounting to between 2.1 and an increase of the possible running distance between 2.4 and 4.6%, and a decrease of the fuel consumption (related to a comparative distance of 100 km.) between 2.3 and 4.3%. Based on further tests a decrease of fuel consumption between 2.3 and 6.2% was found, when compared with results obtained without the additive. The figures obtained show that the results of the comparative measure ments of the fuel consumption with and without additive are in their values well outside the :l% scattering limits obtained with unaltered fuel.

Related to the specific running conditions of the engine using pure commercial gasoline and the measured amount of gas blown through, a decrease of the amount of gas blow through was found, when using gasoline containing the additives of the present invention under the same specific running conditions. The scattering limits of the measurements were 12%, the average percentual decrease rose with rising oil temperature and rising cooling water temperature and reached at 80 C. a figure of 13%. Although it is known, that the results obtained when measuring the amounts of gas blown through tend to oscillate considerably, a distinct decrease within this scattering limit of the amounts of gas blown through was found, when the engine was operated with gasoline containing the additives according to the present invention.

EXAMPLE in the Examples 1-9 were also Daimler-Benz The effects described found in the following bench tests, using a motor 180b.

For the test a super gasoline containing 0.59 cc. per liter lead tetraethyl preparations with an excess content of halogenated hydrocarbons as scavenging agents was used. The gasoline had the following characteristics:

Spec. wt. 0.746 Boiling range, C. 34-196 Boiling to 100 C. percent 46 Content of olefins do 42 Content of aromatics -do 14 Content of benzene do 0 NO. Research 99.5 NC. Motor 87.2

To this gasoline as additive per liter were added in the form of naphthenates: 9.4 mg. Pb, 3.4 mg. Cu, 7.2 mg. Zn.

A special addition of halogenated hydrocarbons could be omitted because of the excess of scavenging agents in the lead preparation.

After an adequate operating period the full effect according to the present invention was revealed.

Summing up it may be stated that comparative determinations of the consumption for operation with and without the additive according to the present invention determined as described above gave, for both experimental series, a consumption reduction of the additive containing gasoline combined with the reduction of the blown through amounts of gas. Reduction of consumption based on consumption without additive amounted to between 2.3 and 6.2%, the reduction of the blown through amounts of gas to a reduction of between 6 and 13%.

Further to the tests described in the above mentioned 10 examples, where the efiicacy of the additive was demonstrated at amounts according to the present invention, other road and bench tests (af) were carried out with gasolines containing additive, which additives although resembling the additive according to the present invention in their components, did not correspond with it in the amounts of Zinc, copper or the halogenated hydrocarbons which were added to each liter of gasoline.

For the road test series (a-d) a Fiat 500-A motor (Topolino) series 1948 was used. The leaded gasoline used for these tests and containing one of the usual halogenated lead tetraethyl preparations had the following characteristics:

Spec. wt. 0.734 Boiling range, C. 35-202 Boiling to C. percent 50 Content of olefins do 21 Content of aromatics do 12 NO. Research 87.4 N.O. Motor 81.0 Lead tetraethyl in cc./l. 0.43

Before the test the car was run with the same gasoline, however not containing the additives, for 500 km. After mechanical cleaning of the motor and after change of the motor oils, the motor was ready for the test. More than 500 km. were driven with the gasoline containing the respective additives. The compression pressure of the cylinders 1-4 were measured before using the gasoline with the additives and after the test.

(a) T est.To the above described gasoline were added as additive in the form of their naphthenates per each liter of fuel: 10.0 mg. Pb, 0.2 mg. Cu, 10.0 mg. Zn. The compression pressure measurements were the following:

Before the test After 630 km.

Cylinder 1 8.6 7. 8 Cylinder 2. 7. 9 7. 4 Cylinder 3.- 8. 6 7. 7 Cylinder 4. 8. 9 8. 2

Upon opening the motor after the test it was found that it was very much smeared and that the piston rings were sticky. The motor head was very much incrusted with a flake-like crust which, however, was easily removable. The cylinder heads 1 and 4 had hard crusts, partly flakes which sprang off when being removed. The cylinder heads 2 and 3, however, showed a compact, smooth ad pitch-tough incrustation.

Any formation of the sealing rings according to the invention was not found at all.

(h) Test.-To the above described gasoline were added as additive in the form of their naphthenates per each liter of fuel: 17.6 mg. Pb, 2.0 mg. Cu, 0.39 mg. Zn.

of fuel: 9.4 mg. Pb, 3.4 mg.

Mercedes 18012 was used.

The results of the compression pressure measurements were the following:

Before the test After 500 km.

Cylinder l. 8.6 8. 2 Cylinder 2- 7.8 7. 6 Cylinder 3. 8. 6 8. 3 Cylinder 4.- 8. 9 8. 6

Upon opening the motor a complete absence of the sealing ring typical for the invention was found. Instead (c) T est.To the above described gasoline were added as additive in the form of their naphthenates per each liter of fuel: 18.0 mg; Pb, 31.5 mg. Cu, 4.2 mg. Zn. The results of the compression pressure measurements were the following:

Before the test After 230 km.

Cylinder 8.6 10. Cylinder 2 7. 8 9. 4 Cylinder 3 8. 9. 3 Cylinder 4".-- 8. 8 10. 0

The test had to be broken off after the first compression pressure measurements were taken because the motor evidently could no longer be subjected to such excessive stress.

Upon opening the motor a thin layer of red ash was found on the piston heads. The cylinder walls were completely dry and without any oil film.

(d) T est.--To the above described gasoline were added as additive in the form of their naphthenates per each liter Cu, 36.0 mg. Zn. The results of the compression pressure measurements were the following:

Before the test After 540 km.

Cylinder 1- 8. 5 8.0 Cylinder 2 7.8 7. 6 Cylinder 3. 8.7 8. 1 Cylinder 4... 9. 0 8.1

Upon running this motor, already after about 100 km. a decrease of the performance was observed and also a frequent and violent knocking of the motor. After opening the motor soot flakes at the plugs and an unusual sooty residue were observed. Furthermore, the measurements before. the opening of the motor showed a decrease of the damaged by the content of Zinc being too high.

Forthe bench test series (e-f) a Daimler-Benz motor (2) T est.-For this bench test described below a gasoline having the following characteristics was used:

Spec. wt. 0.718 .Boiling range, C. 35-162 Boiling to 100 C. percent 66.5 Contentof olefins do 26 Content of aromatics do 11 N.O. Research 89 "-N.0. Motor 80 This gasoline contained only 0.15 cc. per each liter of fuel of one of the usual halogenated lead tetraethyl preparations.

To the above described gasoline were added as additive per each liter of fuel in the form of their naphthenates: 29.4 mg. Pb, 3.4 mg. Cu, 7.2 mg. Zn. There was no spe cial addition of halogenated hydrocarbons.

Because of irregularities which appeared during this bench test with the above named motor and since there was no increase of performance at all, but rather a decrease of performance was observed, the motor was opened. On the piston heads was found a large amount of residues in the form of a grey-white powder which by analysis was found to be lead oxide having a certain content of halides. No tendency for the formation of the metal salt film according to the invention could be 0bserved. This was due to the fact that with the small content of lead tetraethyl preparation too small amounts of halogenated hydrocarbons were present.

(7) T est-For the bench test described below a gasoline was used having the following characteristics:

Spec. wt 0.721 Boiling range, C. 35-167 Boiling to 100 C percent 65 Content of olefins do 28 Content of aromatics do 7 N.O. Research 89.3 N.O. Motor 79.5

amounts of halogenated hydrocarbons as scavenging agents.

To the aforementioned gasoline were added as additive per each liter of fuel in the form of their naphthenates: 29.4 mg. Pb, 3.4 mg. Cu, 7.2 mg. Zn. There was no special addition of halogenated hydrocarbons.

Neither a decrease nor an improvement of performance could positively be observed. The motor was opened and no formation of the metal salt film according to the invention could be observed. There was found, however, only a small precipitation of lead oxide which was regarded as insignificant for the further operation of the motor. The test showed that even with a leading of 0.23 cc. of a leadalkyl preparation per each liter of fuel, a special addition of halogenated hydrocarbons cannot be omitted when the effect according to the invention is to be obtained.

liter,

Without further analysis, the foregoing will so fully reveal the essence of the present invention that others can by applying current knowledge readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention and, therefore, such adaptations should and are intended to be comprehended within the meaning and range of equivalence of the following claims.

What is claimed as new and desired to be secured by Letters Patent is: I

1. A motor fuel for use in internal combustion engines, said motor fuel comprising a liquid hydrocarbon motor fuel for internal combustion engines containing as an essential co-active ingredient an additive per each liter of fuel consisting of about 05-15 mg. of zinc in the form of zinc naphthenate, about 0.5-25 mg. of copper in the form of copper naphthenate, and lead in the form of lead naphthenate in an amount equal to at least two times the total of the zinc and copper content, the total amount of zinc, copper and lead being not more than 200 mg. per and also containing a member selected from the group consisting of brominated and chlorinated benzene and ethylene in an amount sufiicient for an about 10- bromination and an about 20-200% chlorination, respectively, of said copper, Zinc and lead.

2. A motor fuel for use in internal combustion engines,

said motor fuel comprising a liquid hydrocarbon motor fuel for internal combustion engines containing as an essential co-active ingredient an additive for each liter of fuel consisting of about 0.5-15 mg. of zinc in the form of zinc naphthenate, about 0.5-25 mg. of copper in the form of copper naphthenate, and lead in the form of lead naphthenate in an amount equal to about two to three times the total of the zinc and copper content, and also containing a member selected from the group consisting of brominated and chlorinated benzene and ethylene in an amount sufficient for an about 10-100% bromination and an about 20-200% chlorination, respectively, of said copper, zinc and lead.

3. A motor fuel for use in internal combustion engines, said motor fuel comprising a liquid hydrocarbon motor fuel for internal combustion engines containing as an essential co-active ingredient an additive per each liter of fuel consisting of about 0.5-15 mg. of zinc in the form of zinc naphthenate, about 0.5-25 mg. of copper in the form of copper naphthenate, and lead in the form of lead naphthenate in an amount equal to about two to three times the total of the zinc and copper content, and also containing a member selected from the group consisting of brominated and chlorinated benzene and ethylene in an amount sufficient for an about 35-50% bromination and an about 7 -100% chlorination, respectively, of said copper, zinc and lead.

4. A motor fuel for use in internal combustion engines, said motor fuel comprising a liquid hydrocarbon motor fuel for internal combustion engines containing as an essential co-active ingredient an additive per each liter of fuel consisting of about 3.5-8 mg. of zinc in the form of zinc naphthenate, about 0.5- mg. of copper in the form of copper naphthenate, and lead in the form of lead naphthenate in an amount equal to about 2.5-3 times the total of the zinc and copper content per liter, and also containing a member selected from the group consisting of brominated and chlorinated benzene and ethylene in an amount sufficient for an about -100-% bromination and an about 20-200% chlorination, respectively, of said copper, zinc and lead.

5. A motor fuel for use in internal combustion engines, said motor fuel comprising a liquid hydrocarbon motor fuel for internal combustion engines containing as an essential co-active ingredient an additive per each liter of fuel consisting of 3.5-8 mg. of zinc in the form of Zinc naphthenate, about 0.5-5 mg. of copper in the form of copper naphthenate, and lead in the form of lead naphthenate in an amount equal to about 2.5-3 times the total of the zinc and copper content, and also containing a member selected from the group consisting of brominated and chlorinated benzene and ethylene in an amount sufficient for an about 35-50% bromination and an about 70-100% chlorination, respectively, of said copper, zinc and lead.

6. A motor fuel for use in internal combustion engines, said motor fuel comprising a liquid hydrocarbon motor fuel for internal combustion engines containing as an essential co-active ingredient an additive per each liter of fuel consisting of about 7.2 mg. of zinc in the form of zinc naphthenate, about 3.4 mg. of copper in the form of copper naphthenate, about 29.4 mg. of lead in the form of lead naphthenate, and a member selected from the group consisting of brominated and chlorinated benzene and ethylene in an amount sufficient for an about 35-50% bromination and an about 70-100% chlorination, respectively, of said copper, zinc and lead.

7. Diesel fuels, boiling in the range between about 200 F. and about 600 F. containing as an essential oo-active ingredient an additive per each liter of fuel consisting of about 7.2 mg. of zinc in the form of zinc naphthenate, about 3.4 mg. of copper in the form of copper naphthenate, about 29.4 mg. of lead in the form of lead naphthenate, and about 0.045 to about 0.06 cc.

- of mono bromo benzene.

8. A motor fuel for use in internal combustion engines, said motor fuel comprising a liquid hydrocarbon motor fuel for internal combustion engines containing as an essential co-active ingredient an additive per each liter of fuel consisting of about 3.6 mg. of zinc in the form of zinc naphthenate, about 0.6 mg. of copper in the form of copper naphthenate, about 29.4 mg. of lead in the form of lead naphthenate, and about 0.006 cc. of ethylene dibromide and 0.011 cc. of ethylene dichloride.

9. A motor fuel for use in internal combustion engines, said motor fuel comprising a leaded liquid hydrocarbon motor fuel for internal combustion engines containing as an essential co-active ingredient an additive per each liter of fuel consisting of about 0.5-15 mg. of zinc in the form of zinc naphthenate, about 05-25 mg. of copper in the form of copper naphthenate, and lead in the form of lead naphthenate in an amount equal to at least two times the total of the zinc and copper content, the total amount of zinc, copper and lead in the form of naphthenates being between about 3 and 200 mg. per liter, and also containing a member selected from the group consisting of brominated and chlorinated benzene and ethylene in an amount suflicient for an about 10-100-% bromination and an about 20-200% chlorination, respectively, of said copper, zinc and lead in the form of naphthenates.

10. A motor fuel for use in internal combustion engines, said motor fuel comprising a leaded liquid hydrocarbon motor fuel for internal combustion engines containing as an essential co-active ingredient an additive per each liter of fuel consisting of about 3.5-8 mg. of Zinc in the form of zinc naphthenate, about 0.5-5 mg. of copper in the form of copper naphthenate, and lead in the form of lead naphthenate in an amount equal to about 2.5-3 times the total of the zinc and copper content, and also containing a member selected from the group consisting of brominated and chlorinated benzene and ethylene in an amount sufficient for an about 35-50% bromination and an about 70-100% chlorination, respectively, of said copper, zinc and lead in the form of naphthenates.

11. A motor fuel for use in internal combustion engines, said motor fuel comprising a leaded liquid hydrocarbon motor fuel for internal combustion engines containing between about 0.3-0.6 cc. of lead tetraethyl and halogenated hydrocarbon scavenging agents therefor, and also containing as an essential co-active ingredient an additive per each liter of fuel consisting of about 05-15 mg. of Zinc in the form of Zinc naphthenate, about 0.5-25 mg. of copper in the form of copper naphthenate, and lead in the form of lead naphthenate in an amount of about -100% of the total of the zinc and copper content, and also containing a member selected from the group consisting of brominated and chlorinated benzene and ethylene in an amount sufficient for an about 10- bromination and an about 20-200% chlorination, respectively, of said copper, zinc and lead in the form of naphthenates.

12. A motor fuel for use in internal combustion engines, said motor fuel comprising a leaded liquid hydrocarbon motor fuel for internal combustion engines containing per liter 0.3-0.6 cc. of lead tetraethyl and halogenated hydrocarbon scavenging agents therefor in an amount up to 50% higher than necessary for halogenating the lead of the lead tetraethyl, and also containing as an essential co-active ingredient an additive per each liter of fuel consisting of about 3.6 mg. of zinc in the form of zinc naphthenate, about 0.6 mg. of copper in the form of copper naphthenate, and about 10 mg. of lead in the form of lead naphthenate.

13. A motor fuel for use in internal combustion engines, said motor fuel comprising a leaded liquid hydrocarbon motor fuel for internal combustion engines containing per liter between about 0.3-0.6 cc. of lead tetraethyl and halogenated hydrocarbon scavenging agents therefor in an amount up to 50% higher than necessary for halogenating the lead of the lead tetraethyl, and also containing as an essential co-active ingredient an additive per each liter of fuel consisting of about 05-15 mg. of zinc in the form of zinc naphthenate, about 05-25 mg. of copper in the form of copper naphthenate, and lead in the form of lead naphthenate in an amount of about 80-100% of the total of the zinc and copper content in the form of naphthenates.

14. A motor fuel for use in internal combustion engines, said motor fuel comprising a leaded liquid hydrocarbon motor fuel for internal combustion engines containing per liter 0.6 cc. of lead tetraethyl and halogenated hydrocarbon scavenging agents therefor in an amount up to 50% higher than necessary for halogenating the lead of the lead tetraethyl, and also containing as an essential co-active ingredient an additive per each liter of fuel consisting of about 7.2 mg. of zinc in the form of zinc naphthenate, about 0.6 mg. of copper in the form of copper naphthenate, and about 6.2 mg. of lead in the form of lead naphthenate.

References Cited FOREIGN PATENTS 11/1955 France.

DANIEL E. WYMAN, Primary Examiner. Y. H. SMITH, Assistant Examiner.

Claims (1)

1. A MOTOR FUEL FOR USE IN INTERNAL COMBUSTION ENGINES, SAID MOTOR FUEL COMPRISING A LIQUID HYDROCARBON MOTOR FUEL FOR INTERNAL COMBUSTION ENGINES CONTAINING AS AN ESSENTIAL CO-ACTIVE INGREDIENT AN ADDITIVE PER EACH LITER OF FUEL CONSISTING OF ABOUT 0.5-15 MG. OF ZINC IN THE FORM OF ZINC NAPHTHENATE, ABOUT 0.5-25 MG. OF COPPER IN THE FORM OF COPPER NAPHTHENATE AND LEAD IN THE FORM OF LEAD NAPHTHENATE IN AN AMOUNT EQUAL TO AT LEAST TWO TIMES THE TOTAL OF THE ZINC AND COPPER CONTENT, THE TOTAL AMOUNT OF ZINC, COPPER AND LEAD BEING NOT MORE THAN 200 MG. PER LITER, AND ALSO CONTAINING A MEMBER SELECTED FROM THE GROUP CONSISTING OF BROMINATED AND CHLORINATED BENZENE AND ETHYLENE IN AN AMOUNT SUFFICIENT FOR AN ABOUT 10100% BROMINATION AND AN ABOUT 20-200% CHLORINATION, RESPECTIVELY, OF SAID COPPER, ZINC AND LEAD.