BIOFUEL OR ADDITIVE AND METHOD OF MANUFACTURE AND USE

Field

The technology relates to biofiiels containing a high content of biologically derived components. More specifically, the technology relates to biodiesel and spark ignition engine fuels.

Background

Diesel fuels were initially developed using plant-derived oils. Shortly thereafter, petrochemical- based diesel fuels were developed, and remained essentially the only type of diesel fuels that were readily available. In recent years the focus has returned to diesel fuels containing plant-derived oils both as an alternative fuel in areas that do not have access to petrochemicals and as a means of reducing emissions. These, and related diesel fuels are now known as biodiesel.

Biodiesel is defined as mono alkyl esters of long chain fatty acids derived from vegetable or animal fats for use in compression ignition engines. However, most formulations developed and in use rely heavily on a large component being petrochemical-based diesel. For example, Stoldt et al (US

Patent No. 5730029) disclose a fuel composition consisting of at least one low sulfur diesel fuel and esters from the transesterifi cation of at least one animal fat or vegetable oil triglyceride where the preferred content of transesterified oil in the diesel fuel is about 200 to about 5000 parts per million, or less than 0.5%. More recently, the content of transesterified oils has been increased to as high as

20% in commercially available biodiesel formulations.

There are also proposed biodiesel formulations that have higher percentages of plant-derived oils. These exemplify the difficulties in meeting or exceeding the ASTM standards, when attempting to increase the percentage of transesterified oils. For example, US Patent Application Publication Number 20080028671 discloses a "biodiesel" in which the oils are not transesterified. The proposed fuel consists of a vegetable oil comprising between 25 and 75% of the total, petroleum diesel or kerosene, a commercially available fuel stabilizer, and a cetane boost additive. Another proposed fuel consist of 25 to 75 vol. % vegetable oil from which the glycerin has not been removed, 1 to 50 vol. % petroleum diesel, 1 to 50 vol. % turpentine, 0.001 to 5 vol. % fuel stabilizer, and 0.01 to 5 vol. % cetane boost additive. Still another proposed fuel consists of 70 to 98 vol. % vegetable oil, 1 to 20 vol. % petroleum diesel, and 1 to 20 vol. % regular gasoline. The fuel may also include 1 to 20 vol. % turpentine or kerosene. Yet another proposed fuel contains 70 to 98 vol. % vegetable oil, 1 to 40 vol. % ethanol, 1 to 20 vol. % petroleum diesel, and 0.01 to 40 vol. % surfactant. Other

variations include 25 to 75 vol. % vegetable oil in which the glycerin has not been removed, 1 to 50 vol. % petroleum diesel, 1 to 50 vol. % turpentine, 0.001 to 5 vol. % fuel stabilizer, and 0.01 to 5 vol. % cetane boost additive. While it is stated that at least one formulation complies with the current ASTM standards, the flash point cited is well below the accepted minimum for biodiesel and the glycerol content is well above the accepted maximum. Accordingly, the application demonstrates the challenges in meeting the standards set for biodiesel, when attempting to increase the percentage of transesterified oils.

With regard to alternative fuels to replace gasoline in spark ignition engine, numerous formulations have been developed. An example ofsuch a fuel is disclosed in Canadian patent 1340871, in which alcohol is mixed with ether and a lubricant such as mineral oil or a vegetable oil, such as castor oil. Formulations have also been developed for use as alternative fuels that combine renewable carbon sources such as alcohols with fossil fuels. An example ofsuch a fuel is disclosed in Canadian patent 2513001, in which alcohol is mixed with naptha and an aliphatic ester. Similarly, U.S. Patent No. 4,300,912 discloses a synthetic fuel formulation comprising naptha (20-60%), methanol (10-40%), butanol (20-40%) and a colloidal stabilizer that is prepared by heating the formulation in a reactor to a temperature of 300 ° Fahrenheit then passing the resulting vapors through a water cooled condenser and collecting the liquid fuel in a holding tank. U.S. Patent No. 5,575,822 discloses a number of fuel and fuel additives. The fuels range from two component formulations, such as 10 to about 42% terpene, preferably limonene, and from about 1 to about 90% naphtha compound to more complex formulations such as 10 to about 16 w/w % limonene, from about 19 w/w % to about 45 w/w % aliphatic hydrocarbons having a flash point between 7 ⁰ C, to about 24°C, most preferably Varnish Makers and Painters (VM&P) naptha, from about 20 w/w % to about 40% w/w % alcohol, most preferably methanol, from about 9 w/w % to about 36 w/w % surfactant, most preferably glycol ether EB and a preferred fuel comprising about 11.4 w/w % limonene, about 40.7 w/w % VM&P naptha, about 15.5 w/w % glycol ether EB, about 22 w/w % methanol, and about 10.6 w/w % castor oil. Such formulations require significant fuel delivery system modifications. Formulations using methanol degrade conventional fuel lines and seals, such as O rings. Furthermore methanol is corrosive and castor oil, when mixed with methanol, forms deposits within fuel injectors and carburetors that reduce the lifespan of the parts and lead to undue maintenance costs. Also, the relatively high flash point of VM&P naptha results in poor cold starts. Still further, a sufficient amount of at least one surfactant is often required when water is added and/or when methanol is used in combination with limonene in order to form a homogenous or clear solution. Also, when more

than 10 w/w% of limonene is present in the fuel composition, a surfactant is often required. However, even if the fuel contains less than 10 w/w% limonene (or contains water or methanol), a surfactant is still often desirable since it allows the fuel components to blend better and stay blended, thereby increasing the shelf life of the final fuel product.

Whitworth's U.S. Patent No.4,818,250 and 4,915,707 describe a process for purifying limonene for use as a fuel or fuel additive. The process includes distillation of limonene containing oil followed by removal of water. The distilled limonene, blended with an oxidation inhibitor such as p phenylenediamine, is claimed as a gasoline extender when added in amounts up to 20% volume. Unfortunately, in actual testing under a power load in a dynamometer, addition of 20% limonene to unleaded 87 octane gasoline resulted in serious preignition, casting serious questions as to its practical value as a gasoline extender.

Terpenoid based fuels have been disclosed in U.S. Patent No. 5, 186,722. Disclosed are a very wide range of terpenes, terpenoids and derivatives thereof, including limonenes, menthols, linalools, terpinenes, camphenes and carenes. The fuels are produced by a cracking/reduction process or by irradiation. Limonene was shown to produce 84% l-methyl-4-(l-methylethyl) benzene by this process. While the fuel is superior to that of Whitworth, production costs are relatively high.

Eucalyptus oil was explored by Barton and co workers as a fuel additive. Barton and Knight (1997, Chemistry in Australia 64 (1): 4-6) identified commercial solvents and Barton and Tjandra (1988, Fluid phase equilibria 44 : 117- 123 , 1989, Fuel 68:11-17) identified stabilization of petroleum/ethanol fuel blends as potential uses for cineole (from eucalyptus oil). It functions as a co-solvent in fuel blends comprising polar and nonpolar components (petroleum and ethanol for example), thereby preventing phase separation. Cineole is the major component of eucalyptus oil, comprising about 80% of the oil. In other studies, eucalyptus oil was used as a fuel. Performance was very good except that there were problems starting a cold engine on straight eucalyptus oil, which could be readily overcome by adding 20 to 30% alcohol or gasoline.

Various vegetable oils have been added to fuel formulations to increase the lubricity value. For example, U.S. Patent No. 5,730,029 discloses using peanut oil, and other oils having high (80%) oleic acid content, in two-stroke fuels. The combination of a high lubricity value and a high flash point allows for lubrication at high engine temperatures. The flame retarding characteristic of the oil

assists in increasing power. U.S. Patent No. 5,743,923 disclose using peanut oil in conjunction with an alcohol and a petroleum fractional distillate.

U.S. Patent application serial number 10/506963 discloses a fuel additive that is an emulsifying composition that includes a selected ethoxylated alkylphenol, which functions as a surfactant, a fatty acid amide, naphtha and oleic acid. The preferred composition includes one part polyoxyethylene nonylphenol, two parts coconut diethanolamide, two parts heavy naphtha and one part oleic acid, by volume. The invention also extends to a hydrocarbon fuel including the composition.

Summary

Certain disclosed embodiments concern a composition for use as a biofuel or fuel additive. For example, particular disclosed embodiments concern compositions that provide an alternative fuel and a fuel additive that compares favourably to existing fuels with regard to horsepower and torque, for use in spark ignition engines (two stroke and four stroke engines). By selecting the specific components and mixing them in defined ratios, the resulting composition, when combusted, reduces harmful emissions, while increasing gaseous oxygen emission, whether used alone or as a gas additive. Further, by selecting the specific components, a biofuel or fuel additive is provided that contains up to about 56% biologically derived components, all of which are readily renewable. Finally, the remaining about 44% can be produced with a minimum of refining.

In one embodiment, the compositions contain an oxygenated natural aromatic compound.

It was found, surprisingly that the oxygenated natural aromatic compound could be replaced with an oxygenated terpenoid. By selecting the specific components and mixing them in defined ratios, the resulting composition, when combusted, reduces harmful emissions, while increasing gaseous oxygen emission, whether used alone or as a gas additive. Interestingly, non-oxygenated terpenoids did not provide the desired result.

The present technology also provides a biodiesel that contains a very high percentage of biologically derived components. While traditional biodiesels contain up to approximately 20% biologically derived components, in the form of transesterified oils, the present technology provides an exemplary biodiesel containing up to about 60% of at least one transesterified vegetable oil, and about 15% of at least one of an oxygenated terpene, oxygenated terpenoid or oxygenated aromatic natural product,

or at least one terpene or terpenoid having a flash point of at least about 50 ⁰ C, totaling up to as high as about 75% biologically derived components. The high content of natural products leads to very low emissions, especially with regard to nitrogen oxides, sulphur and carbon dioxide. A broad range of oils can be used, including, but not limited to soy oil,Canola™ oil, linseed oil, crambe oil, safflower oil, cottonseed oil, rapeseed oil, peanut oil, algae oil, and corn oil. Similarly, a range of terpenes, terpenoids and oxygenated aromatic natural products can be used, allowing for optimization for given environment, including cold, temperate and tropical environments. The flexibility in formulae also permit optimization of the formula with regard to regional availability of biologically derived components.

Detailed Description

I. Definitions

The following definitions are provided solely to aid the reader. These definitions should not be construed to provide a definition that is narrower in scope than would be apparent to a person of ordinary skill in the art.

A. Vegetable oil: A vegetable oil is a transesterified oil that can be defined as:

(i) being derived from plant material and having a flash point of about 230 ⁰ C to about 343°C, more preferably from about 260 ⁰ C to about 288°C, and still more preferably about 275°C; or (ii) having a C 18 unsaturated fatty acid content of at least about 60%, more preferably at least about 75% and a still more preferably at least about 85% and a viscosity of at least 25 mm ² /s and not greater than about 54 mm ² /s; or

(iii) having an iodine number of at least about 95 to about 140, more preferably from at least about 110 to about 140, still more preferably from about 115 to about 135 and a viscosity of not greater than about 54 mm ; or

(ii) being selected from at least one of Canola™ oil (low erucic acid rapeseed oil), corn oil, flax seed oil (linseed oil), peanut oil, safflower oil, soybean oil, sunflower oil, cottonseed oil, crambe oil, sesame oil, algae oil, and rapeseed oil.

B. Adjustor: Any non-ionic compound that can be defined as:

(i) having a flash point of at least about 90 ⁰ C and more preferably at least about 110 ⁰ C; and

(ii) providing a final viscosity of the fuel between about 1.0 to about 7 mm ² /sec at 40 ⁰ C, more preferably between about 1.5 to about 6.5 mm ² /sec at 40 ⁰ C and still more preferably between about

1.9 to about 6.0 mm ² /sec at 40 ⁰ C. Non-ionic adjusters of the present technology include, but are not limited to, alkyl and aryl substituted oligomers and polymers of ethylene oxide, and polymers of ethylene oxide.

C. Oxygenated natural aromatic compound: Any compound that is a natural product - a product that can be, for example, but not limited to, extracted from a plant, and has at least one hydroxyl, carboxylic acid, aldehyde, ketone, ether or ester functional group, or any and all combinations thereof, coupled to an aromatic ring system, such as a benzene ring, including a substituted benzene ring. The flash point is preferably between from about 60 ⁰ C and about 160 ⁰ C, and more preferably between about 90 ⁰ C and 110 ⁰ C for tropical and temperate environment blends and is preferably between from about 50 ⁰ C to about 90 ⁰ C for cold environment blends. Without being limited to a theory of operation, it currently is believed that oxygenated natural aromatic compounds, in addition to other compounds, as would be known to one skilled in the art, function as combined flame front retarders, anti-corrosive agents and co-solvents. Oxygenated natural aromatic compounds include, but are not limited to, methyl salicylate, eugenol, cinnamaldehyde, and benzaldehyde and their synthetic or natural analogues and derivatives.

D. Selected terpenoid: Any compound comprising repeating isoprene units, including terpenes and terpenoids that can be defined as: (i) having at least one hydroxyl, carboxylic acid, aldehyde, ketone, ether or ester functional group, or any and all combinations thereof, to provide an oxygenated terpene or oxygenated terpenoid; or (ii) having a flash point between about 50 ⁰ C and about 160 ⁰ C, and more preferably between about 90 ⁰ C and 110 ⁰ C for tropical and temperate environment blends and preferably between from about 50 ⁰ C to about 90 ⁰ C for cold environment blends; or (iii) being selected from limonene, cineole, carvone, citronellal, and linalool, and their synthetic or natural analogues and derivatives.

E. Mid-Flash Point Naptha: Mid flash point naptha in the present context, for use in gas-powered engines, has a flashpoint of no greater than about -22 ⁰ C, and more preferably between about -25 ⁰ C and about -35 ⁰ C and is composed of from about 50% v/v to about 99%v/v paraffins and naphthenes, with no greater than about 5% v/v aromatic hydrocarbons, preferably from about 85% v/v to about 99% v/v paraffins and napthenes, with no greater than about 2% v/v aromatic hydrocarbons, and most preferably from about 90%v/v to about 98%v/v paraffins and napthenes with

no greater than 1.5% v/v aromatic hydrocarbons. The following is a non-exhaustive list of terms that refer to materials that would include naptha as defined for use with the present invention: White gas Coleman™ fuel Shellite

Middle distillates Petroleum distillates

F. Mid Flash Point to Low Flash Point Naptha: Any naptha having a flashpoint of no higher than about -22 ⁰ C, and typically having a flash point from a high of about -22 ⁰ C to a low of at least about -50 ⁰ C, and can range from 100% low flash point naptha to 100% mid flash point naptha.

G. Petroleum distillate: Petroleum distillate in the present context is any distillate of petroleum that has a flash point from about 38 ⁰ C to about 70 ⁰ C and a melting point of at most -20 ⁰ C, and preferably -25°C and more preferably, -30 ⁰ C.

H. Pour point: The temperature in Celsius below which a fluid no longer pours freely. The pour point is determined by placing the sample in a jar and decreasing the test temperature.

When the sample does not flow when tilted, the jar is held horizontally for 5 seconds. If it does not flow, 3°C is added to the corresponding temperature and the result is the pour point temperature.

I. High lubricity oil: Lubricity is determined by mixing 4 mL in 996 mL fuel, fueling a 950 watt, two stroke generator motor designed to run on oil and fuel, running the engine at 4,200 RPMS at maximum load for four and one half hours, measuring the compression ratio, and assessing ring stick and scoring of the cylinder walls of the engine. A high lubricity oil is defined as one that does not lead to a reduction in compression ratio, does not create "ring stick" and does not allow scoring under the test conditions.

J. High flash point oil: A high flash (FP) point oil is defined as one having a flash point of about 204 ⁰ C (400 ⁰ F) to about 343°C (650 ⁰ F), more preferably from about 260 ⁰ C (500 ⁰ F) to about 288°C (550 ⁰ F), and still more preferably about 282°C (540 ⁰ F). The following is a non-exhaustive list of oils that would be known to be high flash point lubricating oils: Canola oil, Coconut oil, Corn oil,

Flax seed oil, Olive oil, Peanut oil, Safflower oil, Sesame oil, Soybean oil, Sunflower oil, and Rapeseed oil. Selected mineral oils also have suitably high flash points.

K. High flash point, high lubricity oil: In a present working example, peanut oil is added to the composition. Peanut oil's major component fatty acids are palmitic acid (comprising approximately

1 - 14%), oleic acid (comprising approximately 36-67%), and linoleic acid (comprising approximately

14-46%). An oleic acid content of from about 30% to about 80% provides an acceptable lubricity value, a more acceptable value is obtained with an oleic acid content of from about 40% to about

70% and a still more acceptable value is obtained with an oleic acid content of from about 65% to about 70%. Other long chain fatty acids also provide suitable lubricity values, as would be known to a person of ordinary skill in the art.

L. Alcohol: Alcohols in the present working examples typically are lower alkyl alcohols, such as Cl to C4 alcohols, more specifically methanol, ethanol (95% ethanol), isopropanol, and butanol. As would be known to a person of ordinary skill in the art, other alcohols that are suitable for the present invention include, for example, but not limited to propanol, amyl alcohol, and isoamyl alcohol. The ratio of carbon atoms to hydroxyl functional group should preferably be about 4-to-l , more preferably 3-to-l, and most preferably 2-tol or 1-to-l, to promote solubility in an aqueous environment and to promote miscibility between the polar and non-polar components of the composition. It would be further known to a person of ordinary skill in the art, that any alcohol or mixture of alcohols providing a ratio of between about 1 carbon to about 1 hydroxyl functional group and about 4 carbon to about 1 hydroxyl functional group would be suitable.

M. Low Flash Point Naptha: Naphtha is a group of various volatile flammable liquid hydrocarbon mixtures used primarily as feedstocks in refineries for the reforming process and in the petrochemical industry for the production of olefins in steam crackers. It is also used in solvent applications in the chemical industry. Low flash point naptha is low in paraffins, napthenes and aromatic hydrocarbons. It is predominantly short chain alkanes, preferably C5 and C6 alkanes, more preferably predominately C5 alkanes, and most preferably comprising from about 60% v/v to about 70% v/v C5 alkanes. It may also be known as petroleum ether. Naptha in the present context, for use in gas-powered engines, has a flashpoint of no greater than about -35 ⁰ C, and more preferably between about -40 ⁰ C and about -50 ⁰ C.

N. Low Flash PointPetroleum Distillate: A low flash point petroleum distillate in the present context is any distillate of petroleum that has a flash point from about -22 ⁰ C to about -50 ⁰ C and is comprised of at least one of short chain alkanes (up to about 12 carbons), paraffins and napthenes. Preferably, there is no greater than about 5% v/v aromatic hydrocarbons.

O. Mixture A: Mixture A comprises about 78% oxygenated natural aromatics, including methyl salicylate, cinnamaldehyde, and eugenol.

P. Oil of wintergreen: Oil of wintergreen is methyl salicylate. Without being limited to a theory of operation, it currently is believed that methyl salicylate functions as a combined flame front retarder, anti-corrosive agent and co-solvent. The product is available from ROUGIER PHARMA (DIN 00336211).

Q. Oxygenated terpenoid: Any compound comprising repeating isoprene units, including terpenes and terpenoids that can be defined as:

(i) having at least one hydroxyl, carboxylic acid, aldehyde, ketone, ether or ester functional group, or any and all combinations thereof, to provide an oxygenated terpene or oxygenated terpenoid; or (ii) being selected from cineole, carvone, citronellal, and linalool, and their synthetic or natural analogues and derivatives; and (iii) having a flash point between about 50 ⁰ C and about 160 ⁰ C.

II. Description

An alcohol-based fuel composition has been developed, exemplified in working embodiments by butanol, isopropanol, ethanol and methanol based fuel compositions, which have been developed and tested. Unless otherwise noted, the percentage of each component is on the basis of v/v, regardless of whether the component is liquid or solid. It is a flexible fuel, with a plug in alcohol component. This allows it to be a replacement fuel for 87 octane gas, for use in carbureted engines, and an 89 octane fuel and 91 octane fuel for use in fuel injected engines.

The following table outlines the working range of components contemplated.

Example 1: The composition used is shown in the following table:

Testing by the Industrial Support Fuels and Lubricants Group at the Alberta Research Council provided the following data:

A Zeltex™ octane analyzer reading provided a research octane number of 93.5 and a motor octane number of 85.8. AirCare™ testing was also carried out. The same car was tested under the same operating conditions. The results follow:

Example 2:

M7.5:gas mixes were tested against gas on a 1987 Honda 1600 engine. This engine was chosen as one of the more reliable and commonly-used engines in the four-cylinder automobile line. It was not overhauled although it is well broken-in with more than 26,000 kilometers of use. All pollution controls such as a catalytic converter were removed.

The octane was determined using a Zeltex™ octane analyzer. Emissions were measured in real-time using a Ferret™ emissions tester. The emissions from samples were collected in parallel with testing of the formulae and analyzed by gas chromatography-mass spectroscopy and Fourier Transform Infra Red spectroscopy. The results show an absence of ozone, an absence of aromatics and an absence of formaldehyde. Of the emissions, only the presence of methyl nitrite was remarkable. All run times shown are only relative to the gas standards run on that data collection date.

M7.5: (Octane: 93.5)

M7.5:gas . 30:50

RPM torque HP HC CO O2 CO2 NOX run time ¹

2500 115 23 29.3 .08 5.53 10.63 720 10.76

run time in minutes/L 2Percent of gas emissions 3Percent of gas emissions corrected to 100% run time of gas

M7.5:gas 75:25

run time in minutes/L 2Percent of gas emissions 3Percent of gas emissions corrected to 100% run time of gas

Example 3:

M7.5B was tested against 89 and 92 octane gas on a 1987 Honda 1600 engine. This engine was chosen as one of the more reliable and commonly-used engines in the four-cylinder automobile line. It was not overhauled although it is well broken-in with more than 26,000 kilometres of use. All pollution controls such as a catalytic converter were removed.

The octane was determined using a Zeltex octane analyzer. Emissions were measured in realtime using a Ferret emissions tester. The emissions from samples were collected in parallel with testing of the formulae and analyzed by gas chomatography-mass spectroscopy and Fourier Transform Infra Red spectroscopy. The results show an absence of ozone, an absence of aromatics and an absence of formaldehyde. Of the emissions, only the presence of methyl nitrite was remarkable.

M7.5B

'run time in minutes/L

² Percent of gas emissions

³ Percent of gas emissions corrected to 100% run time of gas

The emissions from samples were collected in parallel with testing of the formulae and analyzed by gas chomatography-mass spectroscopy and Fourier Transform Infra Red spectroscopy. The results show an absence of ozone, an absence of aromatics and an absence of formaldehyde. Of the emissions, only the presence of methyl nitrile was remarkable.

Example 4:

M7.5B

Octane: 89.9

A road test conducted on Terraline™ M with the butanol plug-in (M7.5B) demonstrated that the car ran normally. The vehicle, a Chrysler minivan (fuel injection engine) was first driven on a course that included a 50 km zone, stop signs, a 90 km zone, and a stop light, using 87 octane gas.

The gas was pumped from the system, leaving no more than an estimated .5L in the system. Over 10

L of M7.5B was then put in the system. The car started normally. It was then tested over the same driving conditions, with the exception that it was driven further down the highway and acceleration at highway speed was tested by flooring the accelerator, in addition to standard driving away from a stop light. The driver reported that the driveability of the fuel was the same as that of gas.

Example 5: Other compositions were tested, as follows:

M21

Ran very lean in a carbureted engine and had low emissions, but lower power than M7.5B or

M7.5. M33

Ran very rich in a carbureted engine and had higher emissions than M7.5B or M7.5.

M32

Ran as well as M7.5B, with comparable emissions to M7.5B and M7.5.

M21-W + Mixture A

The results were essentially the same as that for M21.

M34

The results were essentially the same as that for M21 in a carbureted engine, although it ran very lean.

MlO

Ran very well on a carbureted engine.

M3

Ran very well on a carbureted engine.

Example 6:

M15

Emissions were higher than compositions containing Mixture A or methyl salicylate, or cinnamaldehyde. Corrosion was tested in a corrosion test using standard carburetor parts. There was no noticeable corrosion.

Example 7:

Ethanol compositions were tested on a fuel injected engine. The testing included an 87 octane gas sample at the beginning of the testing.

GAS

E21

Could not be tested as the polar and non-polar components were not miscible.

E40B

E41B

E42B

The power output was lower than for the other compositions.

E43B

Power was low.

Example 8:

Further testing involved selecting one ethanol composition and testing it against 87 octane gas in order to determine emissions, run time, and then emissions corrected for run time:

GAS

E7.5B hybrid

Corrected for run time

Example 9:

An isopropanol composition was tested on the fuel injected engine as follows: GAS

I7.5B h brid

Corrected for run time

Example 10:

A butanol composition was tested on a fuel injected engine. The testing included an 87 octane gas sample at the beginning of the testing.

GAS

BlOB

Example 11:

The engine was modified to include a water injection system (TECTANE H2O Injector) and the performance of the fuels was then assessed.

GAS INJECTOR OFF INJECTOR ON

M7.5B h brid

E7.5B hybrid

I7.5B hybrid

INJECTOR OFF INJECTOR ON

Example 12:

A range of oxygenated natural aromatic compounds were tested using one selected composition as follows:

M7.5B h brid

M7.5B h brid eu enol

M7.5B hybrid cinnamaldehyde

Example 13: Emissions and run times were assessed on a select number of compositions. The results were used to assess the utility of each oxygenated natural aromatic compound in the various fuel compositions.

GAS

M7.5B h brid

Corrected for run time

M7.5B h brid eu enol

Corrected for run time

M7.5B h brid salic lic acid

Corrected for run time

Example 14:

A number of compositions were prepared and tested in order to assess the percentage range of each component that could be used. First it was noted that mid flash point naptha could be used interchangeably, or any mixture of the two could also be used. Accordingly, it was thought that any petroleum distillate that has a flash point from about -22 ⁰ C to about -50 °C and is comprised of at least one of short chain alkanes, paraffins and napthenes can also replace naptha. This was studied by replacing the napthas with 87 octane gasoline. Although gasoline is known to contain many additives, the bulk of a typical gasoline consists of hydrocarbons with between 5 and 12 carbon atoms per molecule, and therefore the bulk of a typical gasoline can be considered to be a petroleum distillate. The composition of the fuel and the results were as follows:

Gasoline 7.5B

Emissions

In comparison, gas produced the following test results: GAS Emissions

Although the advantage of the composition was not as great as that using napthas in the composition, there was still a 72% reduction in hydrocarbons, a 45% reduction in carbon monoxide, a 7% reduction in carbon dioxide, a 60% increase in oxygen and a 23% reduction in NOx. It was noted that the engine did not run smoothly and the fuel consumption was high, even though the power output was low. It was concluded that any petroleum distillate that has a flash point from about -22 ⁰ C to about -50 ⁰ C and is comprised of at least one of short chain alkanes, paraffins and napthenes can replace naptha.

Example 15:

Compositions having no peanut oil were compared to those with peanut oil. All formulations were run at 2500 rpm and producing the same torque and horsepower between the samples.

87 Octane gas

Run time 7:59 E7.5B - Honda

Run times were in the range of 7:09 - 7:29

E7.5B/Peanut oil Free - Honda

Run Time 7:13

It is apparent that the peanut oil is not needed in the formulations when a lubricating oil is not an engine requirement - in other words, unless the engine requires a gas:oil mix, as in many two stroke engines and in jet engines, there is no requirement for peanut oil.

Example 16: Formulations using benzaldehyde were also tested and compared with 87 octane gas. Testing was carried out on a carbureted engine. Comparisons were also made with E7.5B. E7.5BE

Percentage of emissions for gas (corrected for run time)

M7.5BE

Percenta e of emissions for as corrected for run time

B7.5BE

Percenta e of emissions for as corrected for run time

Summary of results for compositions containing an oxygenated aromatic compound: Compositions having little or no alcohol could be used as fuels, however, the emissions were not significantly better than the emissions from gasoline. The minimum alcohol content needed to provide a significant reduction in emissions was about 20%, however, as little as 10% alcohol still provided some advantage. The maximum alcohol content was about 45%.

Methanol-based fuels tested ranged from about 23% methanol to about 34% methanol. Blending methanol with isopropanol or butanol allowed the alcohol content to be as high as about 45% (about 35% methanol and about 10% isopropanol or butanol). Note that blending in this context simply refers to preparing a composition that contains both methanol and isopropanol or butanol. If low flash point naptha was used, the methanol content could be increased to about 37% in the presence of about 5% isopropanol or butanol. Also, it would be known that any combination of butanol and isopropanol could be used with methanol to provide essentially the same results.

Ethanol-based fuels tested ranged from about 16% ethanol to 34% ethanol. Blending ethanol with isopropanol or butanol allowed the alcohol content to be as high as 42% (about 34% ethanol and about 8% isopropanol or butanol). Note that blending in this context simply refers to preparing a composition that contains both ethanol and isopropanol or butanol. Also, it would be known that any combination of butanol and isopropanol could be used with ethanol to provide essentially the same results. It would also be known that any combination of ethanol and methanol, wherein the combined percentage ranged from about 16% to about 34%, could be used with isopropanol or butanol or both to provide essentially the same result.

Isopropanol-based fuels tested ranged from about 27% to about 40% isopropanol. Similarly, butanol-based fuels containing up to about 40% butanol were tested. It would be known that any combination of isopropanol and butanol could be used to provide essentially the same results.

The naptha content in the various fuel compositions tested ranged from 44% to about 71%.

Higher naptha content could be used, however the advantage over gas with regard to emissions diminished as the naptha content increased.

The content of oxygenated aromatic compounds tested ranged from a low of 0.25% to a high of about 17%. Isopropanol-based fuels lacking oxygenated aromatic compounds were useable as fuels, however the fuels were corrosive. Similar results would be expected for butanol-based fuels.

In these fuels, an alternative anti-corrosive agent would be required. An ethanol-based fuel lacking oxygenated aromatic compounds was prepared. It was found that trimethyl pentane was required to make the composition useable in a motor vehicle engine. Again, the lack of oxygenated aromatic compound resulted in the fuel being corrosive. Hence, an alternative anti-corrosive agent would be required.

The content of peanut oil tested ranged from 0 to about 2%. Higher amounts could be used, as would be known to one skilled in the art, for example, up to about 5% peanut oil. Transesterified peanut oil was also tested and was considered to be potentially superior to peanut oil in a fuel injection system. Transesterification of any other suitable vegetable oil would similarly be potentially superior to the vegetable oil without transesterification. As would be known to one skilled in the art, a lubricating oil is not necessarily required. Further, oil can be added as needed to the formulations if used in 2 stroke engines, as per the manufacturer's guidelines.

Example 17:

Terpenes that were tested are both oxygenated (carvone, cineole, citronellal) and non- oxygenated (limonene). They vary in flash point as follows: Cineole: 49 ⁰ C

Limonene: 50 ⁰ C Citronellal: 76 ⁰ C Carvone: 88 ⁰ C

The following table shows the NOx as a percent of that emitted from 87 octane gas, using formulations having 55% naptha as follows:

NOx (percent of gas)

The butanol formulations were obviously inferior fuels with regard to NOx. They also had lower 02 and higher CO2 in comparison to the other fuels, although the ratios were better than gas. Formulations comprising from 20 to 70% naptha all showed much higher NOx emissions when limonene was the terpenoid used.

Example 18:

*Ethanol based formulations as follows:

Run times were not significantly different between 87 octane gas, E7.5B and the compositions, as shown above.

Example 19:

All emissions were collected for the formulations above. Those for 55% naptha are presented in the following table. The formulation used was:

The results for the ethanol-based fuel was:

Percentage of emissions relative to gas

The results for the butanol-based fuel were:

Percentage of emissions relative to gas

The results for the methanol-based fuel were:

Percentage of emissions relative to gas

Example 20:

Other formulations were tested including:

NOx emissions were 45% of that for 87 octane gas.

Example 21:

NOx (% of NOx in 87 octane gas emissions)

*E7.5BM was mixed with gas to provide a 10%, 25%, 50%, 75% and 90% mix. Summary of results for compositions containing selected terpenoids:

Compositions having little or no alcohol could be used as fuels, however, the emissions would not be expected to be significantly better than the emissions from gasoline. The minimum alcohol content needed to provide a significant reduction in emissions was probably greater than at least about 23%.

As would be known to one skilled in the art, a lubricating oil is not necessarily required. Further, oil can be added as needed to the formulations if used in 2 stroke engines, as per the manufacturer's guidelines. Nonetheless, it is assumed that about 1 %, more preferably about 2% and most preferably about 5% peanut oil could be added.

The results demonstrate that to obtain a fuel that has superior emissions, especially with regard to NOx, specific components at specific ratios should be employed. Limonene, the only non- oxygenated terpenoid was not suitable for reducing NOx. Similarly, butanol was not the preferred alcohol. Naptha content, to obtain the preferred results, could not be as low as 20%, nor could it be as high as 70%. 20% and 70% naptha led to the engine running very poorly. The preferred range was between about 40% and about 65%, more preferably between 40% and 58.5% and most preferably, between 40% and 55%. The oxygenated terpenoid preferred range was between about 6% and about 21%. Run times were reasonably comparable to those for gas at a given torque and horsepower.

Example 22:

Low temperature biodiesel:

Freezing point -30 ⁰ C

Soy oil can be replaced with any vegetable oil that has a flash point of at least about 270 ⁰ C, more preferably at least about 275 ⁰ C and still more preferably at least about 285 C and a melting point of at most about -17 ⁰ C, more preferably at most about -20 ⁰ C, and most preferably at most about -22 ⁰ C. Limonene can be replaced with any terpenoid that has a melting point of at most about -90 ⁰ C, more preferably at most about -95 ⁰ C. Kerosene can be replaced by any petroleum distillate that has a flash point of at least about 10 ⁰ C and a melting point of not more than -20 ⁰ C, more preferably not more than about -25 ⁰ C, still more preferably not more than about -30 ⁰ C. An adjustor can be added to reduce the viscosity. The adjustor preferably has a comparable flash point or a higher flash point and melting point that is at least as low as the component that is reduced in volume so as to include the adjustor.

Temperate climate biodiesel:

Flash point: 95 ⁰ C Soy oil can be replaced with any vegetable oil or combination of vegetable oils that have a flash point of at least about 270 ⁰ C, more preferably at least about 275 ⁰ C and still more preferably at least about 285 ⁰ C. Methyl salicylate can be replaced with at least one oxygenated natural aromatic compound that has a flash point of at least about 100 ⁰ C. An adjustor can be added to reduce the viscosity. The adjustor preferably has a comparable flash point or a higher flash point as the

component that is reduced in volume so as to include the adjuster .

An example of a composition that includes an adjustor and comprises a mixture of oils is:

Flash point: 94 ⁰ C Cetane: 58

The foregoing is a description of an embodiment of the invention. As would be known to one skilled in the art, variations are contemplated that do not alter the scope of the invention. These include but are not limited to, different combinations of alcohols, different alcohol isomers, derivatives and analogues of oxygenated natural aromatics and derivatives and analogues of oxygenated terpenoids.