WO1999021941A1 - Combustion catalyst and catalyzed fuels with enhanced combustion efficiency and mileage - Google Patents

Abstract

The present invention is directed to combustion catalysts fuel additive compositions, modified fuels exhibiting improved combustion efficiency when modified by an effective amount of the combusiton catalysts; and processes for operating internal combustion engines utilizing the modified fuels. Selected Group IIA and Group IIB metal oxides, hydroxides, and organic peroxides, EMPTM and TBH, which when introduced at ppm levels, into fuels utilized in the internal combustion engines increases efficiency and performance, improves exhaust emissions and reduces carbon deposits and mileage. The combustion catalysts introduction to the internal combustion engine cylinder can be through a suspension within the fuel or as a particulate or liquid suspension introduced through the engine air intake system.

Description

COMBUSTION CATALYST AND CATALYZED FUELS WITH ENHANCED COMBUSTION EFFICIENCY AND MILEAGE

This is a continuation-in-part of application Serial No. 08/960,632 filed on October 29, 1997, still pending. FIELD OF THE INVENTION

The present invention relates generally to modified fuels, fuels exhibiting improved combustion efficiency when modified by an effective amount of combustion catalysts. In another aspect the invention relates to formulations of selected oxides of Group IIA and Group IIB metals and organic compounds which when introduced into fuels utilized in internal combustion engines increases efficiency and performance, reduces wear on moving parts, reduces carbon deposits and improves exhaust emissions. In yet another aspect the invention is related to fuel additive combustion catalyst compositions. This invention also relates to compositions which are additive to liquid and solid fuels to improve their combustion properties. The additive compositions of the present invention are applicable to a variety of such fuels, including distillant fuels, residual fuels, coals or cokes, as well as gasolines and diesels and other like hydrocarbon fuels such as jet fuels. DESCRIPTION OF RELATED ART

The use of fuel additives in an internal combustion engine to improve combustion is well known in the art. For example, it is known in that art that a fuel additive containing various metals may reduce soot buildup in an internal combustion engine and thereby improve combustion. Kukin, U.S. Patent No. 3,348,932, for example, discloses a fuel additive containing combinations of various metals designed to effectively reduce soot buildup.

Other fuel additives for improving combustion efficiency of an internal combustion engine and thereby substantially reducing undesirable motor vehicle exhaust emissions as well as fuel consumption levels is offered by Sanders in U.S. Patent No. 5,266,082. The compositions of the '082 Patent are composed of a bicyclic aromatic components selected from the Group consisting of naphthalene, substituted naphthalene, biphenyl, biphenyl derivatives and mixtures thereof, zinc oxide and at least one Group 8-10 metal oxides selected from the Group consisting of iron oxide, copper oxide, cobalt oxide, ruthenium oxide, osmium oxide and palladium oxide, all dispersed in a carrier liquid. In the preferred embodiments, the. composition contains a mixture of magnesium oxide, zinc oxide and iron oxide all dispersed in a carrier liquid. Exhaust emissions from internal combustion engines present serious environmental concerns. Motor vehicle exhaust emission, in particular, present a serious unchecked problem in many large cities These emissions not only contribute to the smog and pollution problems resulting in the silent continual destruction of the ozone layer and may also cause long term health effects due to their potential toxicity. ln an attempt to regulate the levels of potentially harmful pollutants in the environment, the Environmental Protection Agency propagated emission standards setting forth acceptable levels of carbon monoxide, nitrogen oxides, particulate matter and hydrocarbons in the exhaust emissions of various classes of motor vehicles The hydrocarbon content of vehicle emissions is indicative of the fuel burning efficiency in the engine The higher the percentage of hydrocarbons (HC) emissions, the lower the level of hydrocarbons burned efficiently. The carbon dioxide (C0₂) content of the emissions reflects the combustion efficiency and catalytic action of fuel components in the engine The higher the carbon dioxide contents, the more efficient the combustive process. The carbon monoxide (CO) content of the emissions is also indicative of the level of combustion in the engine chamber A higher level percentage of carbon monoxide in motor vehicle emissions, often caused by lean air to fuel ratio, is indicative of incomplete combustion in the engine chamber The high molecular oxygen (0₂) content in the emissions can mean a lean fuel to air ratio or fouled plugs. Ideally motor exhaust emissions contain low percentages of hydrocarbons, carbon monoxide and molecular oxygen as well as a high percentage of carbon dioxide.

During the last twenty to thirty years vast sums have been spent in an attempt to improve the gas mileage in modern automobile, truck, tractor and marine engine design and fuel research in an attempt to improve fuel utilization. Attempts have been made to operate the engines with lean fuel air mixtures and lead free gasolines as well as modified diesel and two cycle engine fuels. But the efforts have been slow in producing satisfactory results especially due to the Environmental Protection Agency! rules which are tightened on the specific amounts and type^'s of emissions permitted from these vehicles Achieving satisfactory performance by fuel air mixture is not a complete answer in itself, only one of many adjustments which will be required to meet requirements of today and the future as to fuel efficiency utilization and emissions

Fuel additives have been a major focus in these attempts to increase fuel utilization efficiencies Clearly, a need exists to create significant reductions of emissions from a variety of fuels There fuels may comprise for example, any of many grades of hydrocarbons, petroleum products or diesel The introduction of a fuel additive may occur, for example, in a fuel storage tank or in the fuel line or both The fuel additive itself may be in the form of a dry powder, a semi-dry paste or a suspension of particulate matter in carrier liquids, or even a combination of suspension, emulsions and partial solutions In use, it is believed that a chemical reaction takes place between the fuel additives and the fuel, and that the products of the chemical reaction are traced into the fuel in minute molecular form, thereby not only improving the combustion of the fuel but also reducing the friction of moving parts in contact with the fuel Typical fuel modifiers and fuel additives include various organic components such as naphthalene, camphor, taurine and benzoyl alcohol as well as different gasoline fractions To condition the additive, various alcohols and other oxygenated fuel extenders are used in such a way to serve as a fuel substitute resulting in a decreased amount of actual fuel usage especially in the absence of tetraethyl lead and similar other banned additives Stringent diesel emission regulations are also being implemented worldwide and in the

United States, the 1990 Clean Air Act mandates lowering oxides of nitrogen (NOJ emissions to 4 0 grams per horsepower-hour for the 1998 model year The future proposals by the U S Environmental Protection Agency call for further reduction of combined (NOJ and hydrocarbon emissions from heavy trucks and busses to 2 5 g/hp-hr for the 2004 model year Such reductions will require a combination of new engine technology and economically viable new diesel fuels having lower emissions

Creating premium gasoline and diesel fuels with performance additives which meet combustion efficiency goals as well as the E P A mandates is a continuing challenge which has not been completely met by the current available market products Today the use of additives in industrial and other transportation areas is relatively low, and the automotive gasoline and diesel fuel segments will continue to present a strong growth opportunity for additives However, the additives, for example combustion catalysts must satisfy economic, governmental regulations and the reliability demanded by the public, the producer and the

E P A Demand for gasoline and other fuel additives is projected to expand to over ten billion dollars in the year 2000 Also by the year 2000, gains in commodity additives such as oxygenates will nonetheless decelerate since much of the legislative driven growth will already have been garnered While major additive manufacturers provide a variety of high quality additives developed primarily as lubricants, very few of these additives directly address the combustibility characteristics of fuels Hence they have had little or no direct impact on fuel consumption, NO or paniculate matter Instead they increase the amount of smoke and/or other emissions such as hydrocarbons and carbon monoxide-carbon dioxide There is a continuing need by world energy users, particularly with respect to the internal combustion engine, to find fuel additives, fuel blends, and corresponding engine designs and the like which when combined with properly modified fuels and burned in the internal combustion engine cylinder will provide fuel efficiency as well as a friendly environmental emission systems In addition these various elements required for the future internal combustion engine performance must be competitive in pricing for the general public to utilize the engine, and the fuel source As petroleum based-oil fuels diminish due to unavailability and decreased world wide production, combustion efficiency, engine design and the like must be fine tuned and brought to bear in order to fill economic expectations as well as environmental emission standards Only in this way can the petroleum industry provide the consuming public with continuing fuel availability SIJMMARY OF THE INVENTION

The present invention is directed to fuel additive compositions, the modified fuels resulting from the use of fuel additives, and to processes for improving combustion and substantially reducing hydrocarbon, carbon monoxide and molecular oxygen motor exhaust emissions. Combustion catalysts for internal combustion engine fuels which enhance combustion efficiency by substantial reduction of hydrocarbon and carbon monoxide emissions is achieved by utilization of selected oxides of Group IIA and Group IIB elements provided in effective amounts generally in the form of a suspension when combined with a liquid carrier. In accordance with the present invention the catalyzed or modified fuels contain from about 10 to 200 or 300 or greater ppm of the Group IIA or Group IIB element oxides, tertiary butyl hyperoxides, EMPtm s mixed with the metal catalyst oxides to form various modifications of the catalyst. These catalyst when blended with a carrier and added to a fuel have been found to provide the internal combustion engine with improvement of combustion efficiency and demonstrate that the emissions of such modified fuels meet or exceed E.P.A. standards. The fuel additive composition comprises an effective amount of Group IIA and Group IIB metal oxides selected from the Group consisting of zinc oxide, zinc peroxide, zinc hydroxide, strontium oxide, strontium peroxide, calcium oxide, calcium hydroxide and calcium peroxide. These metal oxide or metal hydroxides combustion catalysts have reduced particulate size in order to form suspensions with carrier liquids for direct additive to the end user fuel tank or as an addition to larger storage tanks of the distributor and manufacturer. In other aspects these selected Group IIA and Group IIB metal oxides, tertiary butyl hyperoxides, EMPs mixed with the metal catalyst oxides to form various modifications of the catalyst can be inserted or aspirated into the combustion chamber through other means as a dry particulate matter but for most common usage will be applied as a liquid carrier suspension. The liquid carrier suspension of the combustion catalyst is comprised of at least 90% by weight of a carrier liquid selected from a group of hydrocarbons in the kerosene boiling range as well as other components which can be utilized individually or in combination for example, the C1-C3 monohydrate, dihydrate, or polyhydrate alcohols and mixtures thereof. In addition, various aromatic components such as naphthalene, substituted naphthalene, biphenyl, biphenyl derivatives and mixtures thereof can be utilized as carriers, as well as hosts of hydrocarbon solvents. The choice of liquid metal oxides include not only the common solvents, but also other compounds whose properties render them suitable as solvents or liquid suspension carriers. Hydrocarbon solvents can be arranged in order of increasing chemical complexity under the following major classes: compounds with one type of characteristic atom or Group (hydroxide compounds, esters, halogenated and the like); and compounds with more than one type of characteristic, atom or

Group (ether alcohols, amino alcohols, esters of keto acids and the like). In addition other liquid carriers which possibly do not meet the definition of solvents can be utilized to form suspensions comprised of these liquid media having small solid particles of the metal oxides more or less uniformly dispersed therethrough. If the particles are small enough to pass through ordinary filters, and do not settle out on standing, the suspensions can be called colloidal suspension, however, various physical forms of the suspension including solvents may have other physical chemistry factors which bear on the stability of the suspension as well. Dispersions and colloidal solutions of metal oxides have in recent times found numerous applications in industry, for example, as fuel oil additives, paints and inks. It is an object of the present invention to provide a combustion catalyst for internal combustion engine fuels comprising a stable dispersion having a high content of metal oxides. It is another object of the present invention to provide a combustion catalyst for internal combustion engine fuels which results in fewer emissions and better mileage.

The present invention is also directed to processes for formulating as well as the formulated fuel blends for use in an internal combustion engine comprising providing a hydrocarbon containing fuel for the internal combustion engine and adding to the hydrocarbon containing fuel a fuel additive which is a combustion catalyst comprised of a liquid carrier and selected Group IIA and Group IIB metal oxides (including hydroxides) which when finally divided in particulate size form a suspension with the carrier liquid. In one embodiment the composition contains a zinc oxide, zinc peroxide or zinc hydroxide either blended together or individually or combined with other metal oxides. The additive is added to the hydrocarbon fuel in an amount sufficient to provide a decrease of at least about 50% in hydrocarbon emissions, while substantially reducing the carbon monoxide emission and while increasing carbon dioxide emission from the exhaust system of the internal combustion engine Preferably, the additive is added to hydrocarbon fuel in an amount sufficient to provide a decrease in emission from the exhaust system of at least 50% in hydrocarbon, 20% carbon monoxide, and an increase in carbon dioxide emissions when compared to the corresponding emissions from exhaust systems without the inclusion of the additive In another aspect the fuel additives provide a method for increasing the cetane number of diesel fuels which results in cleaner burning diesel fuels The combustion catalyst additives improve cetane and provide economical improvement in cetane which is less expensive than hydro treatment of diesel fuel which lowers the aromatic content of diesel The combustion catalysts additives according to the invention are chemical cetane improvers and are compounds which at elevated temperatures readily decomposed, and in turn promote the rate of chain initiation, i e emission improvement for diesel fuel

As shown by the following description of the invention, the data contained in the tables and as plotted in the various figures, the combustion catalysts for internal combustion engine fuels which contains a liquid carried, selected oxides of Group IIA and Group IIB clearly demonstrate the modified or catalyzed fuel according to the invention containing effective amounts of the catalysts improves combustion efficiency, reduces hydrocarbon emission, carbon monoxide emissions while in some cases increasing carbon dioxide emissions The combustion catalyst additives according to the invention are suitable for gasoline internal combustion engines, two cycle internal combustion engines and diesel internal combustion engines all of which give improvements in emissions that meet or exceed

E P A standards

BRIEF DESCRIPTION OF THE FIGURES

The graphic presentation of the data contained in the tables are presented in Figures 1 through 22, however, the figure number and table numbers are not correlated For a more complete understanding of the present invention and the advantages thereof, references are now made to the following descriptions taken in conjunction with the accompanying drawings in which Figure 1 presents a comparison of the baseline hydrocarbon emissions for a gasoline engine at idle and at 2000 rpm utilizing regular 86 octane gasoline, the same gasoline, but with E.M P or E Z P additives,

Figure 2 presents a comparison of the baseline carbon monoxide emissions at idle and at 2000 rpm utilizing regular 86 octane gasoline, the same gasoline but with E M.P or E.Z P additives,

Figure 3 is a comparison of the baseline carbon dioxide emissions at idle and at and at 2000 rpm utilizing regular 86 octane gasoline; the same gasoline but with E M P or E Z P additives, Figure 4 presents a comparison of calculated potential mileage increases for the engine at idle and at and at 2000 rpm utilizing regular 86 octane gasoline, the same engine and gasoline with E M P or E Z P additives,

Figure 5 presents carbon monoxide emissions percent before and after use of zinc hydroxide (ZH) catalysts for both idle and high rpm performance, Figure 6 presents hydrocarbon emissions before and after use of zinc hydroxide (ZH) catalysts drawing two idle comparisons and two high rpm studies,

Figure 7 presents carbon dioxide emissions (percent) before and after use of zinc hydroxide (ZH) catalyst additives,

Figure 8 presents carbon monoxide emissions (percent) before and after use of strontium peroxide (STP) catalysts,

Figure 9 presents hydrocarbon emission (ppm) before and after calcium peroxide (CP) additive,

Figure 10 presents carbon monoxide emissions (percent) before and after calcium peroxide (CP) additive at idle and high rpm, Figure 1 1 presents carbon dioxide emissions reduction with calcium peroxide catalysts drawing three idle speed comparisons and three high rpm comparisons,-' DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to fuel additive compositions and processes for improving combustion in internal combustion engines as well as the modified fuels, the result being substantial reductions of potentially hazardous exhaust emissions and mileage. This invention is particularly adapted for reducing the percentages of hydrocarbons, carbon monoxide and molecular oxygen in motor vehicle exhaust emission. Use of the combustion fuel catalyst additive compositions may also result in increased mileage performance as well as an increase in percentage of carbon dioxide in the motor vehicle exhaust emissions. However, with calcium peroxide even the gaseous carbon dioxide emissions are reduced.

FIELD EVALUATION OF THE ADDITIVES EMP™

AND EZP IN MOTOR GRADE GASOLINE

One combination catalyst has been developed and used as a additive, EnviroMax Plus

(EMP™). A second combustion catalyst has been developed for fuel additive, modification,

EnviroZnPeroxide (EZP). In order to test the effectiveness of these products to reduce undesirable exhaust emission and to enhance fuel economy, the following field study was performed to gather data for statistical analysis. The field study utilized seven vehicles of different models and years of manufacture as presented in Table 1. All but one of the test vehicles had both an oxygen sensor and a catalytic converter as their standard pollution prevention equipment. Regular grade, 86 octane gasoline was purchased from five different local retailers and was randomly used for the vehicles as fuel during the study. The goal was to limit the type of gasoline as a variable in the study.

EXPERIMENTAL TEST PROCEDURE

The test protocol involved sampling the tailpipe emissions of the test cars for four different gases HC (hydrocarbons), CO (carbon monoxide), C0₂ (carbon dioxide) and 0₂

(oxygen) It was not possible to measure NO_λ levels in the exhaust with the test sampler used in this study Of the gases that were sampled, those impacting the environment were of the most concern (HC, CO and C0₂) The levels of these three gases in the exhaust were monitored while the engine was running at idle and then at 2000 rpm The cars were first tested randomly on gasoline as it was received from the retail pump The data from these tests are given in Table 2 The vehicle used was not recorded so as not to bias subsequent tests The cars were then refueled, but this time using gasolines and the EMP™ additive

The combustion catalyst EMP™ is EnviroMax Plus which is formulated by blending together by weight 40% naphthalene crystals and 60% powdered zinc oxide (particle diameter< 1 micron) Just enough methanol was added to make a smooth paste Then 250 grams of this naphthalene-zinc oxide paste was added to 32|gallons of solvent mixture It has also been found that the oxides, peroxides and hydroxides of the Group IIA and Group IIB etals of the Periodic Table are good catalysts for use with hydrocarbon fuels to reduce gaseous, tailpipe emissions. However, because some of these metals and their oxides are toxic, only a limited number of the Group II elements can actually be used.

In order to prove the catalatic effects of the inventive additives a sample of zinc hydroxide was obtained, along with samples of magnesium peroxide, calcium peroxide, strontium peroxide, and barium peroxide. Tests with zinc peroxide have shown that the peroxides are the preferred form of these potential combustion catalysts; because the metal peroxides can supply additional oxygen for the combustion process within the cylinder of the engine. The more stable, single oxide form of these metals can also act as an oxygen supply, but the available oxygen in the case of the oxide is only one half that of the peroxide.

Similarly, the hydroxides of these metals can supply the same amount of oxygen as the metal oxide. However, the hydroxides are attractive because of their lower specific gravity versus that of the oxides. Typically, the smaller the specific gravity of the additive, the greater will be the amount and stability of the suspensions in the liquid fuel. Of the Group IIA and Group IIB elements that were tested, the peroxides of zinc, calcium, and strontium were found to be the most effective. Zinc oxide and zinc hydroxide also performed well. However, the other Group IIA and Group IIB elements were either too toxic to be used or too ineffective to be considered as good fuel catalysts. The rejected elements included: beryllium (toxic), magnesium (ineffective), cadmium (toxic), barium (ineffective), mercury (toxic) and radium (toxic).

For emission testing, the oxygen rich Group II elements were suspended in several solvents and the suspension was then added directly to the liquid hydrocarbon fuel. The solvents were blends of ethanol, methanol and VM&P (varnish makers and painters solvent). Concentrations of the metals suspended in the solvents ranged from about five (5) to about 500 ppm or greater by weight. However, the tests also indicated that the metal oxides could be added directly to the liquid fuel without solvents and still be active catalysts. Finally, the tests also indicated that combinations of the metal oxides could be used. Thus calcium peroxide, which was found to be surprisingly effective for the reduction of carbon dioxide, also worked when blended with the zinc oxides.

The solvent mixture contains 5% methanol, 10%> ethanol and 85%>VMP by volume. This suspension or solution of solvents is filtered to remove filterable particulate and the filtrate is bottled as the EMP™ product. In addition other catalyst such as zinc peroxide has been found to very effective in use with fuel blends, gasoline, diesel and the like in increasing performance and promoting a cleaner burn. This catalyst product (EZP) is made the same way that EMP™ is made, except that 2 to 4 grams of zinc peroxide is added to 1 kilogram (32 fluid oz.) of the EMP™ paste, and then added to the solvent mixture. These catalysts are present in the inventive fuel blends in amounts of from about 5 to 10 ppm to about 300 ppm or greater, limited only by separation from suspension. The performance of these catalyst spiked fuels were compared with the performance of a typical consumer gasoline as the baseline. Emission tests were then rerun after a short period of time (10 minutes) to allow equalization and a reasonable expectation that the fuel with the additive had reached the engine. Once again the two different engine speeds (idle and 2,000 rpm) were monitored.

The data for gasoline containing the EMP™ additive are given in Table 3. Finally, the EZP additive was added to the fLiel and the same test procedure repeated. However, because EZP represented a new additive formulation, more test replications were run with this fuel mixture. The data for the gasoline containing the EZP product is given in Table 4. Also shown in all the tables is a column labeled "%> Total Carbon as CO". The values listed under this column represent an estimation of the potential for increased fuel economy. For example, when carbon in the exhaust appears as C0₂, it represents a complete chemical combustion (oxidation) of that part of the carbon originally present in the fuel. The carbon monoxide fraction (CO), however, represents carbon that still has fuel potential for additional combustion. For that matter so does the HC fraction of the exhaust. However, the HC fraction is listed at concentrations of ppm where as the CO is listed as percent. This means that the CO concentration is at least an order of magnitude greater than that of the HC, and hence the CO represents a greater reservoir of untapped chemical energy which went unbumed during its passage through the engine. If the CO in the exhaust would have been completely oxidized to CO,, then a greater fuel economy, i.e. more miles per gallon, would have been realized. Therefore, it was postulated that the percentage of carbon represented as carbon monoxide in the exhaust gases, relative to the total carbon in the exhaust, represented a potential percentage increase in mileage. Thus when the observed CO levels were high, the engine was assumed to be operating with less efficiency, and some fraction of the potential fuel economy was being lost. If the exhaust concentration levels of CO were observed to be low, then the fuel economy was assumed to be near maximum, and the percent levels listed in this column of the tables should approach zero. This approach to the estimation of lost potential fuel economy is considered to be conservative, however. It is conservative because of the presence of a catalytic converter on all newer cars. The intent of having or requiring a catalytic converter is to assist in a more complete oxidation of all products of incomplete combustion in the engine's exhaust. However, since the catalytic converter is installed on the exhaust system after the engine, any combustion that takes place in the converter can not be used in the power producing cycle of the engine Since all the cars but one in this test had catalytic converters, the exhaust concentrations were actually the combination of combustion reactions in both the engine and in the catalytic converter. Therefore, overall, the catalytic converter primarily reduces the HC levels in the engine exhaust and has little if any effect on CO concentration levels. Hence, by considering as we did that only the carbon in the CO in the exhaust gases represents a measure of lost fuel value, then the predictions of potential fuel economy that are listed in the tables should be conservative.

HC Emissions The data in Table 2 suggests that on average slightly more HC is emitted at high rpm than at idle engine speeds However, because of the wide scatter in the data sample, these levels of HC emissions are probably identical The data in Table 3 suggests that with the addition of EMP™ to the gasoline, no improvement over that observed for the regular fuel for the average HC emissions at idle However, the addition of EMP™ to the gasoline did on average produce a 30-35%o decrease in HC emissions at the higher 2,000 rpm Table 3 shows a drop in the averaged HC concentrations of from 124 6 ppm at idle down to 84 9 ppm at 2,000 rpm This is significant even in light of the scatter in the data sample The data in Table 4 suggests that the use of EZP in the fuel was even more successful at reducing HC emissions With the EZP additive the reduction relative to the regular gasoline occurred both when the car was idling or at the 2,000 rpm level In both cases the average HC levels consistently dropped into the 30 to 40 ppm range These low levels, represent on average, a 70%) drop in CO emissions when EZP is added to the fuel This is indeed significant by any measure Because of variations between individual vehicles only average levels of hydrocarbons in the exhaust emissions for each of the different tests was used to prepare 'the graph in Figure 1 This bar graph highlights the significant reduction in IIC levels

CO Emissions The third column of data in Table 2 indicates that for averaged CO emissions there is a significant difference between idle speeds and 2,000 rpm when the regular gasoline was used When the automobile is at idle, CO emissions averaged 0 44% When the engine was turning at 2,000 rpm the CO emissions jumped to more than four times that level, or 1 84%> By contrast, the next table, Table 3, shows that the addition of EMP™ to the fuel resulted in a reversal of the averaged CO emissions between idle and 2,000 rpm In this case, CO emissions dropped from 1 51%> at idle down to 0 95% at 2,000 rpm Overall, these averaged values indicate that the addition of EMP™ during this test did not significantly reduce the CO concentration levels below those which were observed ill the emissions produced with the regular unleaded gasoline However, Table 4 indicates that the addition of EZP to the gasoline did result in the reduction of the CO concentration level in the exhaust gases to 0 44%o at idle and 0 65%> at 2,000 rpm On average this reduction represents a 50% decrease in CO emissions over those observed for the regular gasoline fuels These differences in CO emissions for all the tests are depicted by the bar graph in Figure 2 CQ₂ Emissions

Whenever the HC and CO emission levels are reduced in any combustion process, then the carbon dioxide emission should increase that is unless the additional C0₂ which is being produced is also in some way being removed The potential chemical reactions that are possible with the ingredients in EMP™ and EZP suggest that this could be the case i e that the carbon is removed as a carbonate rather than being emitted as carbon dioxide The data in Tables 2, 3 and 4 suggest that indeed the addition of EMP™ and EZP do increase the averaged percent emissions of CO, over those measured for the regular gasoline alone An average, base level of 10 2% carbon dioxide was recorded for the tests with just regular gasoline The averaged C0₂ level was observed to increase to 12 7% when EMP™ was added to the gasoline, and then rose to an additional averaged value of 13 5% when the EZP was added It should be noted that the maximum C0₂ concentration (on a dry basis) for combustion of a saturated, paraffin hydrocarbon using stoichiometric air is approximately 14 5%o This theoretical level rises to 15% for naphthionic hydrocarbons and to 17% for aromatic hydrocarbon fuels In the experimental tests excess air is typically used Under such lean burning conditions, the theoretically predicted percentages of C0₂ in the exhaust (14 5%,

15% and 17%) should be reduced in the direction of the 13 5% level which was measured Hence, we have concluded that while the use of EMP™ and EZP as additives to gasoline do not reduce the emissions of the "greenhouse" carbon dioxide from internal combustion engines, both additives can reduce the levels of FTC and CO in automobile emissions by increasing the level of combustion of the fuel The bar graph in Figure 3 substantiates this by depicting the increases in carbon dioxide emissions when the additives were utilized Reductions of the magnitudes observed in this study for HC and CO would be significant to improvements being sought to air pollution problems in which HC, CO and NO_x together with UV, can trigger serious health problems in highly congested population areas.

% Total Carbon as CO As mentioned earlier, any increase in vehicle fuel economy should be directly aligned with an overall decrease in vehicle emissions per mile of travel. Thus the last column in

Tables 2, 3 and 4 was generated in an attempt by the investigators to tie any decrease in the CO emissions to a potential percentage increase in fuel economy. This hypothesis is based on the assumption that EMP™ and EZP are both active in the combustion process in the engine; and both are not just assisting the reactions taking place in the catalytic converter. This assumption is also based in part on hearsay reports from users of both products: that the mileage on their cars increased when the additives were being used. The increases in mileage were reported by customers to range from 3% up to 30%. The data in Tables 2, 3 and 4 suggest that on average a 4%> increase in mileage is very probable when EMP™ is utilized and an averaged 6%o increase in mileage would be realized with the use of EZP. The higher potential increases in fuel economy would be possible only when an automobile is not kept well tuned and combustion within the engine is incomplete. Of the seven vehicles in this study, at least one was found to be in need of a tune-up. Hence, with a proper tune and the use of EMP™ or EZP, the operator of that car might realize a step improvement in their fuel economy of greater than 10%. This limited field test has demonstrated the very significant potential derived from the use of the additives EMP™ and EZP in gasoline to reduce undesirable emissions of hydrocarbons (HC) and carbon monoxide (CO). Even though the data were scattered, this conclusion was reached based on comparisons between the averaged values of emissions from seven different cars fueled from five different retail gasoline sources. The study also concludes that these undesirable pollutants can be reduced with a simultaneous increase in fuel economy. This means that the emissions of HC and CO per mile of travel will be even more enhanced and harmful pollution further reduced.

SUSPENDED FUEL CATALYSTS

Data were collected as a result of field studies on twelve different used cars. These cars had never been exposed to catalyst products, and the study represents a one time testing only. In every case, the cars were fueled with regular gasoline. The tailpipe emissions were then recorded with a Sun, four gas analyzer, (HC, CO, C0₂ and 0₂). These data were taken while the cars were stationary: first with the engine running at idle, and then with it running at 2000 rpm. The test samples of the peroxides, oxides, or hydroxides of the selected Group II elements (suspended in ethanol) were then added to the fuel in the gas tank of the car. The cars were then driven for 16 miles and a retest of the tailpipe emissions was performed. The Figures 5-1 1 show the emission levels before and after the addition of the suspended catalysts.

EXPECTED RESULTS

Earlier work with zinc oxide and zinc peroxide indicated that these two additives, when suspended in fuels, crated conditions which produce a more complete combustion of the fuel in internal combustion engines. It was suspected that other Group II elements in the

Periodic Table might also exhibit such behavior. If the oxides of these other elements were successful; then the like with the zinc catalyst, the hydrocarbon and carbon monoxide levels in the exhaust emissions should go down while the carbon dioxide levels in the exhaust increased This outcome is assumed to be indicative of a more complete combustion of the fuel. Figures 5 through 1 1 show the results of the successful test which were observed. If there were no changes in the gaseous emission levels, these data were recorded but not plotted. However, the negative results are noted in the preceding summary However, with calcium peroxide, the carbon dioxide levels in the exhaust emission sometimes went down instead of up. This was attributed to the reaction between calcium oxide with carbon dioxide, produced during combustion, to form calcium carbonate. Hence, a blend of calcium peroxide with zinc peroxide might be used to substantially eliminate most of the harmful and greenhouse gaseous emissions from automobiles. Figure 5 Tests performed with zinc hydroxide (ZH) suspended in ethanol and added to the regular gasoline in the tank Car (1) was an Olds Cierra with 99,389 miles Car (2) was a 1994 Chevy Pickup with 104,250 miles Except for car (1) at high rpm, the zinc hydroxide produced a substantial decrease in the carbon monoxide levels in the exhaust emission The anomaly observed with car (1) at high rpm should disappear after the car is driven greater distances on the ZH fuel catalyst additive

Figure 6 Tests performed with zinc hydroxide (ZH) suspended in ethanol and added to the regular gasoline in the tank Car (1 ) was an Olds Cierra with 99,389 miles Car (2) was a 1994 Chevy Pickup with 104,250 miles In this case except for car (2) at high rpm, the zinc hydroxide produced a substantial decrease in the hydrocarbon levels in the exhaust emission The anomaly observed with car (2) should disappear after the car is driven greater distances on the ZH fuel catalyst additive As with the carbon monoxide, this FIC anomaly is a transient condition which persists until carbon deposits in the engine have been oxidized by the catalyst Figure 7 Tests performed with zinc hydroxide (ZH) suspended in ethanol and added to the regular gasoline in the tank Car (1) was an Olds Cierra with 99,389 miles Car (2) was a 1994 Chevy Pickup with 104,250 miles In this test the zinc hydroxide produced either no change or a slight increase in the carbon dioxide levels in the exhaust emission The anomaly may disappear after the car is driven greater distances on the ZH fuel catalyst additive However, with carbon dioxide the levels can actually decrease if zinc carbonates are formed

Figure 8 Tests performed with strontium peroxide (StP) suspended in ethanol and added to the regular gasoline in the tank The test car was a 1994 Chevrolet Suburban with 102,622 miles In this test the StrP produced a substantial change in the carbon monoxide level only at high rpm There were minimal or no change in other gases

Figure 9 Tests performed with a combination of zinc peroxide and calcium peroxide suspended in ethanol and added to the regular gasoline in Ihe tank The test car was a 1994 Chevrolet Pickup with 161 ,026 miles. In this test the mixed peroxides produced significant reductions of hydrocarbon emissions.

Figure 10: Tests performed with a combination of zinc peroxide and calcium peroxide suspended in ethanol and added to the regular gasoline in the tank. The test car was a 1994 Chevrolet Pickup with 161 ,026 miles. In this test the mixed peroxides produced anomalous results in CO emissions.

Figure 11: Tests performed with calcium peroxide (CP) suspended in ethanol and added to the regular gasoline in the tank. Here the test car (1) was a 1990 Pontiac Grand Prix with

63,918 miles. Test car (2) was a 1987 Dodge Pickup with 188,595 miles. Car (3) was a 1988 Honda Accord with 85,271 miles. In these tests the calcium peroxide produced consistent reductions in C0₂ emissions.

Figure 12: Test were performed on the Dodge Ram 200 Cummins Turbo Diesel before and after catalyst with 4 test being illustrated first being Test #1 with no EMD added, Test #2 adding EMD after ten minutes and Test #3 adding EMD after 1 hour. Test #4 was EMD. Each test showed three runs using low rpm and high rpm respective for carbon monoxide NO and

NO2. Again this was the same Ram 250 Cummins Turbo Diesel using diesel fuel.

Figure 13: Illustrates a comparative study using EM A recommended premium diesel standards and Enviro Max diesel fuel catalyst (EMD). The graphs show flashpoint and degrees F, cloud point, cetane number and lubricity for the four different fuel blends including EMA FQP#1 and EMA FQP#2, a baseline diesel and diesel plus EMD. EMD is one of the additives as defined by this application for being part of the invention. Therefore, diesel plus EMD is a modified fuel.

Figure 14: Illustrates a comparison of carbon dioxide emissions at idle and 2000 rpm using a baseline EMP™ and EZP according to the invention. The same Dodge 250 Cummins Diesel was utilized for the test. As can be seen, the carbon monoxide was reduced from base levels, levels using EMP™ to the lowest test results of a fuel modified the EMP™ and EZP.

Such a reduction in carbon monoxide emissions is desirable both at idle and running speed.

Figure 15: Illustrates a comparison of carbon monoxide emissions at idle and 2,000 rpm using baseline, EMP™, and EZP.

Figure 16: Illustrates a comparison of hydrocarbon emissions at idle and 2000 RPM using a baseline, EZP, and EMP™; using the same Dodge 250 Cummins engine for these test. Hydrocarbon emissions are the least when using the additive in most cases at least 50% reduction or greater. Figure 17: Illustrates a comparison of coal carbon emissions at idle and 2000 rpm using a baseline EMP™ and EZP are shown. The carbon percent for the EMP™ and the EZP is the smallest of the three groups when using EMP™ and EZP additives.

Figure 18: Illustrates a NO/NO2 ratio using pemex diesel and EMD. The pemex diesel and EMD evaluations were lower for NO/N02 ppm than any of the baseline test. Figure 19: Illustrates a carbon monoxide emission using pemex diesel and EMD. The diesel and EMD provided CO/ppm which were less in every case than the two baseline test.

Figure 20: Illustrates for the same diesel Dodge pickup particle matter emission using pemex diesel and EMD versus two different baselines. After sufficient pemex diesel and EMD was run through the vehicle, significant reduction in particle matter emission was achieved. Figure 21: The international 7.3 liter diesel (VVT72P) showed a significant increase in fuel economy (MPG) using either TBH or TBH plus EMP™ or TBH, EMP™ and EZP. A baseline with no additive achieved 8.51 miles per gallon while the best additive being TBH and

I EMP™ achieved 11.21 miles per gallon.

Figure 22: Illustrates a GMC 6.6 liter diesel truck (PAN1768) achieved a maximum 11.48 miles per gallon for 38.15 increase over a baseline where no additive was added to the fuel in Test 1. Test 2 showed a reduction using TBH. Test 3 showed a similar or greater reduction using only TBH in the fuel. However, Test 4 using TBH/EMP™ in Test 5 TBH,

EMP™ and EZP showed significant increases of 26.35 % increase in miles per gallon or 38.15 % increase per miles per gallon.

PROPERTY EVALUATIONS FOR GASOLINE WITH THE ADDITIVE EMP™ OR EZP

Because the practice of refining crude oil to produce and improve the quality of motor gasoline has been extensively developed over the last several decades, a number of standard tests to measure quality have evolved. These tests have become routine to the extent that they have received ASTM designations and/or, in the case of corrosion, the test have been sanctioned by

NACE (National Association of Corrosion Engineers). Since the additives EMP™ and EZP are added to motor fuels as a means decreasing emissions and increasing engine performance, it seemed appropriate to subject blends of gasoline and diesel with EMP™ and EZP to several of the more common laboratory tests. Core Laboratories of Houston, Texas was selected as an independent laboratory and requested to perform the ten tests listed in Table 6.

The attached data sheets and graphs give core laboratory's finding from these ten tests Their results are summarized here It should be kept in mind that the active ingredients in both EMP™ and EZP are solid particulate matter which has been suspended in selected solvents prior to addition to the liquid fuel By design the concentration of suspended solids should not exceed 10 ppm In fact the "particulate matter" test (ASTM - D-2276) indicates that there was only 1 to 2 mg per liter (ppm) in the gasoline sample which were tested Regular, pump grade gasoline by companson was shown to have concentration of particulate matter of less than 0 1 mg per liter

Because the additives represent such a small fraction of the fuel blend, the property of "fuel ash content" by ASTM - D-482, and the "fire and flash point" characteristics by ASTM - D-92 of the pump grade gasoline were found to be unaffected by either additive Flowever, both of the additives appear to decrease the "heat of combustion" level for the fuel by 1%) The change in this property, which is indicative of the energy content of the gasoline, may not be significant overall if the particulate catalysts actually provide more complete combustion in the engine. Other tests on the gaseous emissions from engines with fuels containing EMP™ and EZP appear to confirm that more complete combustion of the fuel does in fact occur when the additives are present.

With respect to the Ried Vapor Pressure (ASTM - D-5191), the EZP product caused and increase of just over 7% in RVP, while the EMP™ produced no change at all. Generally, the lower the RVP the less volatile the fuel, and the lower the amount of fugitive emissions of hydrocarbons form the fuel. The EZP also produced much higher levels of peroxide in the tested gasoline blends in which EZP was used. This was not unexpected; since EZP technology is based on the use of a peroxide as a catalyst. The only major concern with peroxides in the fuel is that any cracked fractions of the gasoline (unsaturated aliphatic hydrocarbons) may polymerize and form resin deposits. However, these same peroxides in an aromatic based fuel can help open the aromatic ring structures and prevent carbon deposit formation in the engine. Hence, EMP™ and EZP might be tailored for different types of fuels; if the fuel analysis is known. The EMP™ product also appeared to be more effective at increasing "research octane" and "research cetane" levels of the fuels in which were tested. It is still not understood as to how or why this increase takes place. Moreover, the increase generated by the use of EMP™ did not occur with the higher, premium octane grades of gasoline. This might imply that the solvents used with EMP™ and EZP produce the observed octane and cetane increases

Finally, the addition of EMP™ and EZP to regular U.S., pump grade gasoline does not appear to change the ASTM - D-86 distillation test. However, the Pemex regular grade gasoline had a flattened area over the range of 20% and 50% distillation This flatten area was removed by the addition of EMP™ and EZP to a more favorable linear increase. This change implies that the Pemex gasoline should perform better in the engine when EMP™ or

EZP is added.

The above data while being inconclusive should further be compared with cetane

ASTM D-613 analysis of commercially available diesel which gave a cetane number of 47.6 The same diesel fuel utilizing ZP (zinc peroxide) and TP8 (tertary butyl hydroperoxide) raised the cetane number to 63 7 In addition, a second commercially available diesel sample treated with zinc peroxide and tertary butyl hydroperoxide provided a cetane number of 73 1 These tests clearly indicate that the combinations in zinc peroxide and an organic peroxide as an additive to diesel yield substantial increases in cetane which is most desirable. In addition, Pemex diesel without additive provided a cetane number of 51 0 and yet when provided with an additive of zinc peroxide and tertary butyl hydroperoxide yielded a cetane number of 73.1. Clearly the combination of a metal oxide additive with an organic peroxide utilized in combination with commercially available diesel supply increases cetane numbers substantially as much as 53%

STUDIES OF FILTERS

A Ford Econoline E350 Diesel Van was used to test the effectiveness of fuel additive ZP for reduction of particulate emissions This vehicle had approximately 63,000 miles on its odometer and a thirty gallon fuel tank The van's gas tank was filled with commercial , pump-grade diesel fuel from a local Lubbock, Texas retail outlet The Van was driven in normal street traffic to warm up the engine Following this warm up period, the particulate exhaust emissions from the tailpipe were captured with a high volumetric filter at an isokinetic air velocity The particulate matter was first captured at an idle engine speed and then again at a high engine rpm However, the Van was stationary at all times during these tests Once these background data had been collected, the ZP fuel additive was added to the

Van's fuel tank The additive consisted of 8 ounces of an ethanol carrier containing the zinc peroxide (ZP) catalyst at a concentration of 200 ppm The Van was again driven in city traffic for fifteen minutes to make sure that the additive and the fuel were reasonably well blended After this stabilization period the particulate matter in the exhaust was again sampled at the isokinetic air velocities associated with idle (30 mph) and high (60 mph) rpm engine speeds

The filters used in these tests were 8" x 11 " sheets of Whatman No 1882-866 These filters consist of random mats of pure borosilicate glass fibers which enable detailed chemical analysis of trace pollutants with minimal interference and background The filters have been heat treated to remove any residual organic traces and are rated at a 99 99% efficiency for

DOP 0 3 micron sized particles The filters were especially developed for high volume air sampling of atmospheric particles and aerosols and are approved by EPA Microscopy The test filters with the exhaust debris attached were sent to SemTech, Inc. For microscopy analysis. Each filter had a 3/8-inch diameter sample cut from a random location on the filter. These samples were then mounted with carbon tape on individual stubs with the appropriate side up and examined at 400X to 600X. Particle sizing , energy dispersive X-ray analysis spectra (EDX), and scanning electron microscopy (SEM) were performed on each sample. The specific instrument used for these measurements was an Hitachi S-2460N Scanning Electron Microscope interfaced with a calibrated NORAN Voyager III X-ray/image analysis system. The data from the microscopy studies were reduced to indicate the number of particles per square mm of the filter surface captured during a thirty minute test. Several individual particles were also analyzed for chemical composition. The average length to width ratio of the particles was also determined, and these are also shown in Table 8. This table indicates that the use of the additive generated a 60% reduction in the numbers of particles in the exhaust for an idle engine rpm and a 30% reduction at high rpm. The L/W ratio indicated that the particles produced prior to the additive had higher aspect ratios indicative of rod or stick like shapes, while the particles produced after the additive was used were more spherical or elliptical in shape. As expected, the high engine rpm levels with the higher isokinetic velocities always produced more particles on the filter surfaces which were skewed towards larger average particle sizes.

In both cases, with and without the additive, the particles were found to consist primarily of oxides and other minerals of iron, sulfur, phosphorous, and copper. These elements are common to the additives used in diesel fuels, or to the metallurgy of the engine. For example, sulfur and phosphorous can be found in the fuel, while iron and copper are common wear metals from engine components. Another study has shown that the use of the ZP additive can reduce the amount of wear metals formed during engine operation while the levels of sulphur and phosphorous remain dependent on the fuel being used.

Finally, as noted above, the lower engine rpms produced particles with smaller size distributions, while the exhaust velocities at the higher rpms were capable of sweeping more and larger sized particles out of the exhaust system. This is a kinetic energy effect in which more and larger particles are entrained and translated at the higher velocity. Also shown in Table 8 for comparison purposes are the same types of data taken from a vehicle fueled on regular unleaded gasoline. In this case the numbers of particles are greatly reduced for gasoline versus diesel, and the additive was found to actually add to the particulate emissions at low rpm engine speeds

ANALYSIS OF FILTER SAMPLES

Nine other samples were glass fiber filters identified as #l -#8 and E520 Elemental analysis and the size distribution were to be performed on a random selection of particulates on the filters

METHOD OF INVESTIGATION

Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray analysis (EDX) were performed using a Hitachi S-2460N Scanning Electron Microscope interfaced with a Noran Voyager III X-ray/image analysis system The microscope and the NORAN voyager III system were calibrated prior to particle size measurement. The results of the particle size measurements were tabulated and plotted using an Excel spreadsheet.

DETAILS OF INVESTIGATION The samples 1-8 and E520 were examined for the constituent elements of particulates on the glass fiber filters. Each of the nine filter samples had one 3/8-inch diameter pieces taken randomly from the filter. Samples were mounted with carbon tape on individual stubs with the appropriate side up. Each specimen was examined at 400X - 600X. The area of the field was calculated according to the magnification used. Particle sizing and EDX spectra were made of 10 to 20 fields in each of the nine samples. Table 10 shows the elements present in particulates found on the respective 9 filters. The last entry are the background elemental constituents of an unused, clean area on a glass fiber filter

The shaded area in Table 10 are elements found in the glass fiber filter In order to distinguish these background elements from the particulates found on the filter, each spectra collected had the background elements' peaks subtracted form each EDX spectrum to the degree consistent with the amount found in background control spectnim The remaining peaks, even elements previously identified as background elements, are a true depiction of the constituent elements of a particulate

Particulate size distribution was determined using the Noran Voyager image analysis software Images were converted to a binary format and then adjusted so that only the particulate binary images remained The software then determined the area, length, and width dimensions of the particulates This process was followed for images from all filters Table 1 1 shows the averages for each of the nine Groups - 3 i

The data of Table 12 indicates that new oil is relatively clean Of the eight (8) metals examined in the test, zinc, copper and iron appear to be the biggest contributors to contaminated oil However as can be seen the iron contamination is reduced substantially through the use of E M P after 3000 miles as is zinc and copper Differences in oils, equipment, locations and operations prohibit a simple guideline for establishing where metal limits will fall. However, significant increase*,- -from one sample to the next of five (5) to ten

(10) ppm or 100% , whichever is greater, should prompt concern. One should also be reminded that zinc is considered to be an antiwear additive and is typically utilized in the industry as an additive for lubrication purposes. On the other hand, most iron complex particulate material is generally quite hard (used as a polishing powder) and creates wear problems through its presence in the lubricating oil.

Outboard marine two cycle engines were tested utilizing EnviroMax Plus fuel catalyst.

The initial deposit results of a small 9.9 horsepower, two stroke outboard engine utilizing EMP™ additive were most encouraging. After four (4) hours of engine service utilizing oil-gasoline blend, treated with EMP™ at the rate of one (1) fluid ounce per five (5) gallons of blend fuel, the combustion chambers of the two cycle engines as well as piston tops of the two cycle engine which was a used engine at the beginning, were cleaner and drier. The exhaust system was clean and dry with the complete disapperance of the normally oily deposits. The combustion catalyst additives in accordance with the present invention were most suitable for enhancing cleaner burn with less emissions even in two cycle engines as indicated by the two cycle used engine evaluation test.

Table 13 shows the use of Phillips Petroleum Diesel on June 8 and June 10, 1988 in a 1991 Dodge Ram 250 Cummins Turbo Diesel. Test 1 had no product or additive added to the diesel fuel that was purchased through local stations in Lubbock, Texas. A baseline of Test 1 shows the emissions and miles traveled at a constant speed. The test included idle speed emission test as well as emissions at 2000 RMP. Test 1 ,2 and 3 represent baseline (no additive) testing. Test 4 used 1.25 ounces of TBH as additive as indicated with a 13.8 % improvement

I on MPL. Test 5 was ended abruptly because of driver miscalculation but showed a 10.81 % improvement on MPL with 1.25 ounces of EMP™ added to the fuel. Test 6 showed a 17.7% improvement on MPL using 1.25 ounces of EMP™. In Test 7, 12.99% improvement in MPL based on 1.75 ounces of TBH and 1.25 ounces of EMP™ as additive. One can see also an average at 2000 RPM of carbon monoxide and other emission efficiencies.

TABLE 13

Phillips Petroleum Diesel - June 8th - June 10th, 1998

Test Specifications:

Vehicle: 1991 Dodge RAM250 Cummins Turbo Diesel

Fuel: Phillips Petroleum Diesel

Fuel Per Run: 25 Liters

Emissions: ECOM America AC Plus 6 Gas Analyzer & Diagnosticator

Test m Baseline (No Additive)

Beginning Mileage: 89,516

Ending Mileage: 89,623

Miles Traveled: 106.4

MPL: 5.420

Product Added: none

Emissions: see chart below

Emissions IDLE 2000 RPM

Temp. Air (Fahrenheit) 89 _89

Temp. Gas (Fahrenheit) 97_ 109

02 % 18,7 % _18,3 %

CO ppm 243 ppm 549 ppm

NO ppm 188 ppm 103 ppm

N02 ppm 105 ppm 132 ppm

NOx ppm 293 ppm 235 ppm

SQ2 0 00 ppm 0 00 ppm

CxHy % 0 02 % 0 06 %

CQ2 % 1.7 % 2 0 '

Efficiency % 98.6 %o 97.1 ° i

Losses % 1 4 % 2.9 %

Exc. Air 9 13 Z1A1Ϊ

Test #2 Baseline (No Additive)

Beginning Mileage: 89,623

Ending Mileage: 89,729

Miles Traveled: 106.4

MPL: 5.353

Product Added: none

Emissions: see chart below

Emissions IDLE 2000 RPM

Temp. Air (Fahrenheit) 93 93 Temp. Gas (Fahrenheit) 115 130

02 % 18.8 % l-L-1

CQ ppm 23JLppm 541 ppm

NQ pm 216 ppm 121 ppm

N02 ppm 116 ppm 150 ppm

NOx ppm . 332 ppm _271 ppm

S02 ppm 0.00 ppm 0.00 ppm

CxHy % 0.05 % 0.06 %

C02 % h& U_%

Efficiency % 96.1 % 94.2 %

Losses % 3.9 % 5.8 %

Exc. Air 9.5 %AQ

Test #3 Baseline (No Additive).

Beginning Mileage: 89,729

Ending Mileage: 89,835

Miles Traveled: 106.4

MPL: 5.256

Product Added: none

Emissions: see chart below

Emissions IDLE 2000 RPM

Temp, Air (Fahrenheit) 24 95^*.

Temp. Gas (Fahrenheit) 137 L42

Q2 % 18.7 % 18.3 %

CO ppm 264 ppm 536 ppm

NQ ppm 209 ppm . L21_ppm

NQ2 ppm . 117 ppm 129 ppm

NQx. ppm 326 ppm 250 ppm

SQ2 ppm 0.00 ppm 0.00 ppm

CxHy % 0.04 % 0.09 %

CQ2 % 12Z 2.0 %

Efficiency % 92.7 % 92,] %

Losses % 7.3 % I

Exc. Air -U UΑ

Test #4

Beginning Mileage: 89,729

Ending Mileage: 89,942

Miles Traveled: 1064

MPL: 5.981 (13.80% improvement)

Product Added: 1.25 oz TBH Emissions: see chart below Emissions IDLE 2000 RPM

Temp. Air (Fahrenheit) _82. 31

Temp. Gas (Fahrenheit) _L4i ZL5A

02 % 18.7 % 18.3 %

CO ppm 217 ppm 419 ppm

-NO ppm 176 ppm 1 1 ppm

N02 ppm 100 ppm 123 ppm

NOx ppm 276 ppm .241 ppm

SQ2 ppm 0.00 ppm 0 00 ppm

CxHy % 0.03 % 0.07 %

CQ2 %_ 1.7 % 2,0 %

Efficiency % 89.6 % 89.5

Losses % 10.4 ' 10.5

Exc. Air 9.13 LIΆ

Test #5

Beginning Mileage: 89,949 Ending Mileage: 90,047 Miles Traveled: 97.9 MPL: 5.824 (10.81% improvement)

Product Added: 1.25 oz EMP Emissions: none taken, vehicle was brought in early due to driver miscalculation.

Test #6

Beginning Mileage: 90,047 Ending Mileage: 90,154 Miles Traveled: 106.3 MPL: 6.188 (17.73% improvement)

Product Added: 1.25 oz EMP Emissions: see chart below

Emissions IDLE 2000 RPM

Temp Air (Fahrenheit) 9_8_ _9_£

Temp Gas (Fahrenheit) 151 165

02 % 18.7 % 18.3 %

CO ppm 214 ppm 445 ppm

NQ ppm.. 218 ppm 151 ppm

_NO2 ppm 99 ppm

NQx ppm 317 ppm 283 ppm

SQ2 ppm 0.00 ppm 0 00 ppm _CxHyZ _ 0 03 % 0.06 % CQ2 % 1.7 % -2,0 %

Losses % 9,1% 9,8 %

Exc, Air 9.13 7.78

Beginning Mileage: 90,154 Ending Mileage: 90,260 Miles Traveled: 106.4 MPL: 5.939 (12.99% Improvement)

Product Added: 1.75 oz. TBH, 125 oz. EMP Emissions: see chart below

Emissions IDLE 2000 RPM

Temp. Air (Fahrenheit) _&£. Z&l

Temp, Gas (Fahrenheit) 126 126

02% 18,6% 18.4%

C ppm 227 ppm 372 ppm

N ppm 158 ppm 109 ppm

NQ2 ppm 97 ppm 113 ppm

255 ppm _222 ppm

SQ2 ppm 0.00 ppm 000 ppm

CxHy % 0,03 % 004 %

CQ2 % 1.8% 1,9%

Efficiency % 93.3 % 93.8'

Losses % 6,7 % 6,2 % Exc. Air 8.75 8.08

Table 14 shows a comparative study of EMA premium diesel standards and enviromax diesel fuel catalyst standards, baseline, EMP-diesel. Included in the four test are flashpoints- percent maximum, cetane numbers and particulate matter for the four items as the last indication of emission control. Table 14 is self explanatory and represents a full study of emissions.

Comparative Study: EMA Premium Diesel Standards and Enviro Max Diesel Fuel Catalyst (Standards, Baseline, EMP-D)

EMA FQP #1 EMA FQP #2 Baseline Diesel Diesel + EMD

Flash Point- eg F 100.00 126.00 88.0000 Water PPM max 200.00 200.00 208.0000

Distillation-Deg. F a) 90% max t .2.00 630.00 588.0000 b) 95% max 550.00 671.00 615.0000

Kinematic Viscosity 1.85 3.00 ^* *J CA> 2.3300

Ash % max 0.01 0.01 Λ r, n ""> 0.0010

Sulfur % max 0.05 0.05 0.0316

Copper Corrosion max 3.00 3.00 σs ι I . V U V v ι

— . ι_ _ 1.0000

Cetane Number min 50.00 50.00 51.3000

Cetane Index min 45.00 45.00 46.3000

Carbon Residue, RAMS 0.15 0.15 ^•*-^■ A ^Λ 0.3000

API Gravity max 43.00 39.00 C ,^**( fι ^{* *}"* 35.1000

Lubricity g. min 3,100.00 3,100.00 Lubricity Wear Test 510.0000

Stability insolubles 15.00 15,00 1.1000 Cloud Point-Deg. F ^Λ l Ac ^! 4.0000 Particle Matter 10.00 10.00 i ,OvUu 5.2000

Kinematic Viscosity is an average of the ranges given.

Lubricity was given by two different standards, each acceptable.

Cloud Point is the responsibility of the fuel supplier; no standard given.

Table 15 following is a mileage indication for an internal combustion engine having 7.0 liter diesel engine VVT72P and shows mileage improvements when using the various additives according to the invention. A baseline is also indicated with four independent test using components of the additives and additives according to the invention with strong results showing percent improvement of at least 31.72 % as a highest percent improvement on mileage for test 4 however, test 2 did indicate a negative percent increase of 2.4 % .

Table 16 following includes a GMC 6.6 liter diesel truck PAN 1768 illustrating miles per gallon for a baseline in various additives according to the invention. There were two negative test, Test 2 and 3, however again a test 4 and 5 showed positive results which were in the 26.3 % improvement and 38.15 % improvement in mileage for the diesel vehicle.

GMC 6.6 Liter Diesel Truck PAN1768

Miles Per Gallon

While the present invention has been described in detail with reference to specific examples, it would be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and the scope of the invention.

Claims

WHAT IS CLAIMED IS

1 Combustion catalysts for internal combustion engine fuel which enhance combustion efficiency by reduction of hydrocarbon and carbon monoxide emissions, compπsing an effective amount of at least one Group IIA and Group IIB oxides selected from the Group consisting of zinc oxide, zinc peroxide, zinc hydroxide, strontium oxide, strontium peroxide, strontium hydroxide, calcium oxide calcium peroxide and calcium hydroxide, and sufficient liquid carrier to keep the catalyst in suspension for addition to the internal combustion engine fuel

2 The combustion catalyst according to Claim 1 wherein the effective amount of Group II A and Group IIB oxides is from about five (5) ppm to 100 ppm to 200 ppm or greater based on the internal combustion fuel presence

3 The combustion catalyst according to Claim 2 wherein the presence of the combustion catalyst is limited by the carrier's suspension limits which maintains the effective amount of Group IIA and Group IIB metal oxides in suspension with the internal combustion engine fuel

4 The combustion catalvst according to Claim 1 which is comprised of zinc oxide in suspension with sufficient amount of liquid hydrocarbon carrier

5 The combustion catalyst according to Claim 1 wherein the catalyst is comprised of zinc peroxide in suspension with sufficient amount of liquid hvdrocarbon carrier 6 The combustion catalvst according to Claim 1 wherein the catalyst is comprised of zinc hydroxide in suspension with sufficient amount of liquid hydrocarbon carrier

7 The combustion catalyst according to Claim 1 wherein the the catalyst is comprised of at least one of a Group IIA and Group IIB oxides selected from the Group consisting of zinc oxide, zinc peroxide, zinc hydroxide, calcium oxide, calcium peroxide and calcium hydroxide

8 The combustion catalyst according to Claim 7 wherein the catalyst is comprised of zinc peroxide and calcium peroxide m suspension with sufficient amount of liquid hydrocarbon carrier The combustion catalyst according to Claim 1 wherein the internal combustion engine fuel is comprised of gasoline The combustion catalyst according to Claim 1 wherein the internal combustion engine fuel is comprised of diesel The combustion catalyst according to Claim 1 wherein the internal combustion engine fuel is comprised of two cycle oil-gasoline blend The catalyst for internal combustion engines according to Claim 1 wherein the carrier is comprised of liquid hydrocarbons from a Group of hydrocarbon fraction in the kerosine boiling range as well as other components which can be utilized individually or in combination selected from the Group consisting of the C,, C₂, C₃ monohydrate, hydrate or polyhydrate alcohols The combustion catalyst according to Claim 12 wherein the liquid hydrocarbons are further selected from the Group consisting of aromatic components such as naphthalene, substituted naphthalene, biphenyl, biphenyl derivatives and hydrocarbon solvents The combustion catalyst according to Claim 1 wherein the liquid carrier aromatic components are comprised of VMP solvent The combustion catalyst according to Claim 1 wherein the liquid carrier comprises at least 90% by weight of the catalyst carrier suspension and is selected from the Group consisting of hydrocarbon fraction in the kerosene boiling range having a flashpoint of at least 100°F in and an auto ignition temperature of at least 400°F, a C,-C₃ monohydrate, dihydrate, or polyhydrate aliphatic alcohol and mixtures thereof The combustion catalyst according to Claim 1 wherein the hydrocarbon emissions are reduced by up to 50% and the carbon monoxide emissions are reduced upward of 30% The combustion catalyst for internal combustion engines according to Claim 10 wheretn the diesel cetane number is increased by at least 10% by utilization of at least one of the Group IIA and Group IIB selected oxides and an organic peroxide The combustion catalyst according to Claim 17 wherein the organic peroxide is comprised of tertary butyl hydroperoxide The combustion catalyst according to Claim 1 wherein the catalvst when combined with internal combustion engine fuel provides enhanced combustion efficiency with ignition particulate size reduction The combustion catalyst according to Claim 1 wherein the cataK st is comprised of calcium oxides and zinc oxides in a hydrocarbon liquid carrier suspension which reduces hydrocarbon and carbon monoxide emissions as well as reduction of carbon dioxide emission The formulated fuel for internal combustion engines which enhance combustion efficiency by reduction of hydrocarbon and carbon monoxide emissions comprising providing a hydrocarbon containing fuel for said internal combustion engines, adding to said hydrocarbon containing fuel combustion catalysts comprising

(a) a liquid carrier compused of a bicyclic aromatic component selected from the Group consisting of naphthalene, substituted naphthalene, biphenyl, biphenyl derivatives and mixtures thereof and

(b) a Group IIA and Group HB oxide selected from the Group consisting of zinc oxide, zinc peroxide, zinc hydroxide, strontium oxide, strontium peroxide, strontium hydroxide, calcium oxide calcium peroxide and calcium hydroxide The catalyst for internal combustion engines according to Claim 21 wherein the liquid carrier is further comprised of liquid hydrocarbons from a Group of hydrocarbon fraction in the kerosine boiling range as well as other components which can be utilized individually or in combination selected from the Group consisting of the C,, C₂, C₃ monohydrate, hydrate or polyhydrate alcohols The formulated fuel according to Claim 21 wherein the fuel is comprised of gasoline The formulated fuel according to Claim 21 wherein the fuel is comprised of diesel The formulated fuel according to Claim 21 wherein the fuel is comprised of two cycle fuel blend The formulated fuel according to Claim 21 wherein by adding said fuel combustion catalysts to said hydrocarbon containing fuel in an amount to provide a decrease in emissions from the exhaust system of at least 50% in hydrocarbon and up to 30% carbon monoxide emissions when compared with the emissions in hvdrocarbon fluid fuel without the additive combustion catalvst The formulated fuel according to Claim 26 wherein the combustion catalyst suspension is added in an amount to provide a decrease in molecular oxygen emissions from said exhaust system of at least 10% when compared with the corresponding emissions from said exhaust system without the inclusion of the combustion catalyst suspension In the operation of an internal combustion engine having associated therewith a fuel chamber from which fuel is supplied to said engine and exhaust system for emission of combustion products from said engine, the process comprising providing said fuel chamber a hydrocarbon containing fuel suitable for use in said internal combustion engine, and providing in said fuel chamber a fuel containing an effective amount of a combustion catalyst comprised of a suspension of liquid hydrocarbons carrier and selected Group IIA and Group IIB metal oxides selected from the Group consisting of zinc oxide, zinc peroxide zinc hydroxide, strontium oxide, strontium peroxide, strontium hydroxide, calcium oxide, calcium peroxide and calcium hydroxide in effective amounts to provide a decrease in emissions from the exhaust system of said internal combustion engine of up to 50% in hydrocarbons and at least 20% or greater carbon monoxide emissions when compared with the corresponding emissions from said exhaust system of a base condition involving use of said hydrocarbon fuel without the inclusion of the suspension of combustion catalysts The process of Claim 28 wherein the carrier is comprised of a bicyclic aromatic component selected from the Group consisting of naphthalene, substituted naphthalene, biphenyl, biphenyl deπvatives and mixtures thereof The process of Claim 28 wherein said metal oxides are supplied to said fuel chamber in a carrier liquid selected from the Group consisting of hydrocarbon fraction in the kerosene boiling range and a C_rC₃ monohvdrate, dihydrate or polyhydrate aliphatic alcohol and mixtures thereof The process of Claim 28 wherein the metal oxides is zinc oxide The process of Claim 28 wherein the metal oxides is zinc peroxide

33. Combustion catalysts for internal combustion engine fuel which enhance combustion efficiency and mileage, reduction of hydrocarbon and carbon monoxide emissions and mileage improvement, comprising an effective amount of at least one Group IIA and Group IIB oxides selected from the Group consisting of zinc oxide, zinc peroxide, zinc hydroxide, strontium oxide, strontium peroxide, strontium hydroxide, calcium oxide, calcium peroxide and calcium hydroxide; TBH and EMP™; and sufficient liquid carrier to keep the catalyst in suspension for addition to the internal combustion engine fuel.

34. The combustion catalyst according to Claim 33 wherein the effective amount of Group IIA and Group IIB oxides is from about two (2) ppm to about 200 ppm or greater based on the internal combustion fuel presence; an organic peroxide varying from about two (2) ppm to about 200 ppm or greater based on internal combustion fuel present.

35. The combustion catalyst according to Claim 33 which is comprised of zinc oxide in suspension with sufficient amount of liquid hydrocarbon carrier.

36. The combustion catalyst according to Claim 33 wherein the catalyst is comprised of at least one zinc peroxide, calcium peroxide, TBH and EMP™, in suspension with sufficient amount of liquid hydrocarbon carrier.

37. The combustion catalyst according to Claim 33 wherein the internal combustion engine fuel is comprised of diesel.

38. The catalyst for internal combustion engines according to Claim 33 wherein the carrier is comprised of liquid hydrocarbons from a Group of hydrocarbon fraction in the kerosine boiling range as well as other components which can be utilized individually or in combination selected from the Group consisting of the C,, C₂, C₃ monohydrate or polyhydrate alcohols.

39. The combustion catalyst according to Claim 38 wherein the liquid hydrocarbons are further selected from the Group consisting of aromatic components such as naphthalene, substituted naphthalene, biphenyl, biphenyl derivatives and other hydrocarbon solvents. 40. The combustion catalyst according to Claim 39 wherein the liquid carrier aromatic components are comprised of VMP solvent.

41. The combustion catalyst according to Claim 33 wherein the hydrocarbon emissions are reduced by up to 50% and the carbon monoxide emissions are reduced upward of 30% and mileage is increased by at least 8% ,

42. The combustion catalyst according to Claim 37 wherein the diesel cetane number is increased by at least 10% by utilization of at least one of the Group IIA and Group IIB selected oxides, TBH and EMP™.

43. The combustion catalyst according to Claim 33 wherein the catalyst is comprised of at least one calcium oxides, zinc oxides, TBH and EMP™, in a hydrocarbon liquid carrier suspension which reduces hydrocarbon and carbon monoxide emissions as well as reduction of carbon dioxide emission.

44. The combustion catalyst of Claim 33 wherein the metal oxides is zinc peroxide and TBH.