WO2007036678A1

WO2007036678A1 - Fuel compositions containing fuel additive

Info

Publication number: WO2007036678A1
Application number: PCT/GB2005/003760
Authority: WO
Inventors: Ian David Hurst
Original assignee: International Fuel Technology, Inc.
Priority date: 2005-09-30
Filing date: 2005-09-30
Publication date: 2007-04-05
Also published as: US20090049740A1; EP1945742A1; AU2006296396A1; CA2624046A1; CN101356255B; BRPI0616796A2; CN101356255A; WO2007036742A1

Abstract

A fuel composition consisting of at least 95% by weight of predominantly or entirely hydrocarbon liquid fuel and 0.001 to 5.0% by weight of fuel additive, wherein the additive consists of: a) 20 to 90% by weight of at least one alkoxylated alcohol corresponding to Formula (I) b) 40 to 10% by weight of at least one polyalkylene glycol ester corresponding to the following general Formula (II) c) 40 to 0% by weight of at least one alkanolamide corresponding to the following general Formula ((III) Provide that the sum of (a), (b) and, when present (c), constitutes 100% by weight of said fuel additive present in the fuel composition

Description

FUEL COMPOSITIONS CONTAINING FUEL ADDITIVE

With ever increasing fuel costs, such as petroleum based fuel costs, it has become ever more important and commercially desirable to consider and improve fuel economy within combustion processes, particularly within automotive powering combustion processes. Gasoline and diesel are the most prominent petroleum distillate-derived fuels used for motive power in vehicular transport. It is widely known that the fuel efficiency of a compression ignition engine is typically better than in a comparable spark ignition engine. It is also desirable to improve efficiencies within internal combustion engines but especially within diesel compression ignition engines by reducing, minimising or potentially avoiding build-up of deposits upon fuel injector components.

Diesel engines present a problem for the automotive and transportation industry because exhaust emissions typically include high levels of particulate matter (PM) together with oxides of nitrogen (NO_x) Diesel engine particulate emissions can be visible in the form of black smoke exhaust. Currently, diesel engine particulate matter emissions can be controlled by the use of black smoke filters or catalytic converters. While these emission-control devices can be effective in decreasing particulate matter emissions, they are not effective in reducing NO_x emissions and may have an adverse effect upon fuel economy.

Compression ignition engines have been tested using multiple different fuels from varying petroleum based feedstocks. In selecting a fuel composition, the effects of that composition upon several factors should be evaluated. Among these factors are engine performance (including efficiency and emissions), cost of end product, necessary infrastructure changes to produce the components of the composition and availability of feedstock to provide those components.

In different parts of the world, incentives are available for cleaner burning fuels to replace "classic" diesel. In Europe, the EN 590 specification diesel is characterised by an initial boiling point of 170⁰C and a final boiling point of 590°C. The preferred sulphur content is less than 50 ppm. In the US there are, essentially, 2 different specifications. An EPO specification and a CARB specification diesel with less than 500 ppm sulphur requirements. The difference in the two specifications is aromatic content and distillation boiling point ranges.

Over the next decade it is expected that it will be desirable even further to decrease the amount of sulphur in diesel fuel. However, decreases in fuel sulphur content generally decreases lubricity of the fuel leading to increased engine wear and may adversely affect fuel economy and/or deposit accumulation upon fuel injector components.

One possible alternative or supplement to ordinary diesel is biodiesel. Biodiesel is a non-toxic, biodegradable replacement for petroleum diesel, made from vegetable oil, recycled cooking oil and tallow. Biodiesel belongs to a family of fatty acids called methyl esters defined by medium length, C₁₆-C₁₈ fatty acid linked chains. These linked chains help differentiate biodiesel from regular petroleum distillate-derived diesel. Biodiesel has performance characteristics similar to conventional petroleum-based diesel but can be cleaner burning.

Blends of biodiesel and petroleum-based diesel can reduce particle, hydrocarbon and carbon monoxide emissions compared with conventional diesel. Direct benefits associated with the use of biodiesel in a 20% blend with conventional petroleum-distillate derived diesel as opposed to using straight diesel, include increasing the fuel's cetane and lubricity for improved economy and engine life and reducing the fuel's emissions profile for CO, CO₂, PM and HC and/or reductions in fuel injector deposits.

However, biodiesel is expensive to manufacture and may not help reduce NO_x emissions. Some biodiesels, in fact, exacerbate NO_x emissions.

It is a purpose of this invention to mitigate the above-problems and to use predominantly hydrocarbon-liquid fuel feedstocks currently available through the existing refinery and distribution infrastructures, optionally blended with known alternative non petroleum distillate predominantly hydrocarbon fuels.

A further purpose of the invention is to provide a method for improving fuel efficiency and/or reducing internal fouling deposits in engines operated at average ambient temperatures above 0⁰C.

These and other purposes are achieved by devising fuel compositions utilising hydrocarbon fuel such as petroleum-derived gasoline, diesel or kerosene incorporating an additive blend of two or three key components, generally as set out in Claim 1 herein. In some embodiments, the fuel composition may include a fraction of synthetic blend derived from natural gas condensate. Such useful fuel compositions can be high lubricity, high cetane fuel. However, certain bio- diesel blends have been known to create extra NO_x emissions.

It has now surprisingly been found that fuel economy can be improved and/or injector fouling can be alleviated by using fuel compositions containing no more than two or at most three fuel additive components within ranges of selected relative proportions as defined within the text of e.g. Claim 1. Some preferred embodiments of fuel additive blends for particular fuel compositions are to be found in Table 1 , at the end of this description.

Referring to the fuel additive in the ethoxylated alcohol (a) component, it is preferred that R¹ is C₉ or Cio and x is 2.5. The additive may, for example, contain 30 to 80% of ethoxylated alcohol. In some embodiments, the additive includes 40 to 60% ethoxylated alcohol component, and in other embodiments 50% to 60%by weight of (a) as defined in Claim 1. In some embodiments it is preferred that the amount of (a) exceeds the sum of (b) and (c). This may particularly be the case for kerosene (heating oil) compositions and diesel fuel compositions. It may also be preferred within additive blends for diesel fuel compositions, that the alkanolamide component (c) may be absent, in such embodiments, the fuel additive then still consists of (a) plus (b).

In the polyethylene glycol ester component (b), preferably R³ is C₁₇ and R⁵ is COR³. Polyethylene glycol diesters of oleic acid are preferred, as are polyethylene glycol ditallates, although the corresponding mono-oleates can be used. The preferred polyethylene glycol ester component (b) may include blends of different such glycol esters of the same general formula. In some embodiments the additive includes from about 40 to 15%, and in other embodiments 35% to 25% of polyethylene glycol ester constituent, and in further embodiments 30% to 25% by weight of (b).

In the alkanolamide component (c), when present, preferably R⁶ is C₁₇ and R⁷ is CH₂CH₂OH. Oleic acid diethanolamides are highly preferred. The ethanolamide component may be a blend of different alkanolamides corresponding to the general formula III. In some embodiments, the additive includes 40% to about 15%, in other embodiments 25% to 15% by weight of alkanolamide.

As used throughout the specification and claims, terms such as "between 6 and 16 carbon atoms," "C₆" and C_6-16" are used to designate carbon atom chains of varying lengths within the range and to indicate that various conformations are acceptable including branched, cyclic and linear conformations. The terms are further intended to designate that various degrees of saturation are acceptable. Moreover, it is readily known to those of skill in the art that designation of a component as including, for example, "Ci₇" or "2.5 moles of ethoxylation" means that the component has a distribution with the major fraction at the stated range and therefore, such a designation does not exclude the possibility that other species exist within the distribution.

Ethoxylated alcohols can be prepared by alkoxylation of linear or branched chain alcohols with commercially available alkylene oxides, such as ethylene oxide ("EO") or propylene oxide ("PO") or mixtures thereof.

Ethoxyiated alcohols suitable for use in the invention are available from Tomah Products, Inc. of 337 Vincent Street, Milton, Wisconsin 53563 under the trade name of Tomadol™. Preferred Tomadol™ products include Tomadol 91-2.5 and Tomadol 1-3. Tomadol™ 91-2.5 is a mixture of C₉, C₁₀ and C₁₁ alcohols with an average of 2.7 moles of ethylene oxide per mole of alcohol. The HLB value (Hydrophyllic/Lipophyllic Balance) of Tomadol™ 91-2.5 is reported as 8.5. Tomadol™ 1-3 is an ethoxylated C₁₁ (major proportion) alcohol with an average of 3 moles of ethylene oxide per mole of alcohol. The HLB value is reported as 8.7.

Other sources of ethoxylated alcohols include Huntsman Corp., Salt Lake City, UT, Condea Vista Company, Houston, TX and Rhodia, Inc., Cranbury, NJ.

The monoester (b) can be manufactured by alkoxylation of a fatty acid (such as oleic acid, linoleic acid, coco fatty acid, etc.) with EO, PO or mixtures thereof. The diesters can be prepared by the reaction of a polyethylene glycol with two molar equivalents of a fatty acid.

Preferred polyethylene glycol esters (b) are PEG 400 dioleate, which is available from Lambent Technologies Inc. of Skokie, IL, as Lumulse 41-0 and PEG 600 dioleate, also available from Lambent as Lumulse 62-0. Another polyethylene glycol ester (b) suitable for use in the invention includes Mapeg brands 400-DOT and 600-DOT and/or Polyethylene glycol 600 ditallate from BASF Corporation, Speciality Chemicals, Mt. Olive, NJ. Other suppliers of these chemicals are Stepan Co., Lonza, Inc. and Goldschmidt, AG of Hopewell, VA.

Generally, the alkanolamide(s) (c) can be prepared by reacting a mono- or diethanolamide with a fatty acid ester. A preferred alkanolamide is oleic diethanolamide. Alkanolamides suitable for use in the invention are available from Mclntyre Group, University Park, IL under the trade name of Mackamide. One example is Mackamide MO, "Oleamide DEA". Henkel Canada is another commercial source of suitable alkanolamides such as Comperlan OD, Oleamide DEA". Other commercial sources of alkanolamides are Rhodia, Inc. and Goldschmidt AG.

The components of fuel additive can be mixed in any order using conventional mixing devices. Ordinarily, the mixing will be done at ambient temperatures from about 0°C to 35°C. Normally, the fuel additive can be splash blended into the base fuel. Ideally, the fuel additive will be a homogeneous mixture of each of its components.

Preferably, the fuel composition will comprise from about 0.001 to 5% by weight, preferably 0.001 to 3% or 0.01 to 3% of the fuel additive composition.

Fuel compositions according to the invention exclude the presence of other non specified or non defined fuel additive components within the present 'closed¹ definition of the term "fuel additive".

It is also within the scope of this invention to provide a method of increasing the fuel economy efficiency of predominantly petroleum distillate fuels.

EXAMPLES

The following examples are intended to illustrate, but not in any way limit, the invention. Various blends were made to compare the characteristics of the various blends of fuel with performance in fuel efficiency (i.e. miles per gallon or mpg).

Reference is now made to the accompanying Figure 1 which is a graph showing the average miles per gallon comparison between base fuel (unadditised) and additised fuel from buses tested according to Example 3 below. EXAMPLE 1

Background:

The test was carried out to investigate the effect that Sample D1 had on the fuel consumption of an indirect injection diesel engine under standard test conditions. The formation of deposits on the injector nozzles of the engine was also investigated.

Test Description:

The test was performed under the standard conditions of test procedure CEC F-23-A-01 , Issue 11. Fuel consumption was measured by Mass Flow Rate and expressed in Kg/Hr.

Injector nozzle fouling results are expressed in terms of the percentage airflow loss at various injector needle lift points. Airflow measurements were accomplished with an airflow rig complying with ISO 4010.

Test Engine:

The engine used for the test was a Peugeot XUD9AL unit supplied by PSA specifically for the Nozzle Coking Test, as originally specified by CEC Working Group PF-23.

Engine part number: 70100

Swept volume: 1.9 litre

Injection pump: Roto Diesel DCP R 84 43 B910A

Injector body: Lucas LCR 67307

Injector nozzle: Lucas RDNO SDC 6850 (unflatted)

Firing order: I, 3, 4, 2 (No. 1 at flywheel end)

Engine Build and Item Preparation:

The injector nozzles were cleaned and checked for airflow at 0.05, 0.1 , 0.2, 0.3 and 0.4 mm lift. The nozzles were discarded if the airflow was outside of the range 250 ml/min to 320 ml/min. The nozzles were assembled into the injector bodies and opening pressures set to 115±bar.

Test Fuel:

Reference fuel CEC RF-06-03 was used throughout the study. Additive Formulation: Sample D1 is a blend consisting of:

50% Ethoxylated alcohol (Tomadol 91-2.5) - (a) 25% Polyethylene glycol diester (PEG 400 DOT) - (b) 25% Diethanolamide (Mackamide MO) - (c) The fuel component was diesel fuel.

Initial Test Preparation:

A slave set of injectors were fitted to the engine. The previous test fuel was drained from the system. The engine was then run for 25 minutes in order to flush through the system. During this time all the spill-off fuel was discarded and not returned. The engine was then set to test speed and load and all specified parameters checked and adjusted to the test specification. The slave injectors were then replaced with the test units.

Engine Warm-Up:

5 minutes, idle speed at no load.

10 minutes, 2000 rev/min 34 Nm torque.

10 minutes, 3000 rev/min at 50 Nm torque.

Test Operating Conditions:

Immediately after the warm-up the following test cycle was run 134 times giving a total test time of 10 hours and 3 minutes.

Other Operating Parameters:

Test Procedure:

The CEC F-23-A-01 test was performed through two test cycles; Test Cycle 1 : Ref. IF-XUD9-001.

This test cycle was performed with reference fuel unadditised with Sample D1. Test was commenced with clean test injector nozzles as per the standard test procedure. Fuel flow was recorded throughout the test cycle. At completion of test cycle, injector nozzles' flow rates were measured and recorded.

Test Cycle 2: Ref: IF-XUD9-002.

The test cycle was then performed with reference fuel additised with Sample D1 at a dose rate of 1 part Sample D1 : 600 parts fuel, vol/vol. The test was commenced with clean injector nozzles as per the standard test procedure. Fuel flow was recorded throughout the test cycle. At completion of the test cycle, injector nozzles' flow rates were measured and recorded. Test Results:

Test Number: IFT-XUD9-001 Fuel Code: RF-06-03 Additive Code: Sample D1 Treat Rate: N/A

Test Number: IF-XUD9-002 Fuel Code: RF-06-03 Additive Code: Sample D1 Treat Rate: 1 PART in 600

Summary of Test Results:

Fuel Flow Test Results:

Injector Nozzle Fouling Test Results:

% Nozzle fouling after Test Cycle 1 , IF-XUD9-001 88%

% Nozzle fouling after Test Cycle 2, IF-XUD9-002 89%

Conclusions:

1) The fuel flow rate results indicate that the addition of Sample D1 to the reference diesel at a dose of 1 :600 vol/vol to reference fuel results in a reduction in fuel consumption over standard test conditions. The largest improvement in fuel economy was seen at the lowest rpm setting. The smallest improvement in fuel economy was seen at the highest rpm setting.

2) The injector nozzle fouling test results indicate that addition of Sample D1 at a dose rate of 1 :600 vol/vol to reference fuel does not result in increased deposits.

EXAMPLE 2

Background:

The test was carried out to investigate the effect that Sample D1 as used in Example 1 above had on the formation of deposits of injector nozzles of an indirect injection diesel engine.

Test Description:

The test was performed to the test procedure CEC F-23-A-01 , Issue 11. Results are expressed in terms of the percentage airflow loss at various injector needle lift points. Airflow measurements were accomplished with an airflow rig complying with ISO 4010.

Test Engine:

Engine part number: 70100

Swept volume: 1.9 litre

Injection pump: Roto Diesel DCP R 8443 B910A

Injector body: Lucas LCR 67307

Injector nozzle: Lucas RDNO SDC 6850 (unflatted) Firing order: I, 3, 4, 2 (No. 1 at flywheel end).

Engine Build and Item Preparation:

The injector nozzles were cleaned and checked for airflow at 0.05, 0.1 , 0.2, 0.3 and 0.4 mm lift. The nozzles were discarded if the airflow was outside of the range 250 ml/min to 320 ml/min. The nozzles were assembled into the injector bodies and opening pressures set to 115± bar.

Test Fuel

Reference fuel CEC RF-93-T-095 was used throughout the study. Note that this reference fuel is specifically blended to encourage deposit formation.

Initial Test Preparation:

Engine Warm-Up:

5 minutes, idle speed at no load.

10 minutes, 2000 rev/min 34 Nm torque.

10 minutes, 3000 rev/min at 50 Nm torque.

Test Operating Conditions:

Other Operating Parameters:

Test Procedure:

The CEC F-23-A-01 test was performed through three test cycles; Test Cycle 1 : Ref. IF-XUD9-003.

This test cycle was performed with reference fuel unadditised with Sample D1. Test was commenced with clean test injector nozzle. At completion of test cycle, injector nozzles' flow rates were measured and recorded.

Test Cycle 2: Ref. IF-XUD9-004.

Engine prepared as per test procedure but the dirty injector nozzles from Cycle 1 were returned to the engine unclean. The test cycle was then performed with reference fuel additised with Sample D1 at a dose rate of 1 part Sample D1 : 600 parts fuel, vol/vol. At completion of the test cycle, injector nozzles' flow rates wee measured and recorded.

Test Cycle 3: Ref. IF-XUD9-005.

Repeat of the test Cycle 2 procedure with the dirty injector nozzles returned to the engine unclean after flow rate measurement at the end of Cycle 2.

On completion of the third test cycle the test results were analysed for observed effects on injector nozzle fouling by the addition of Sample D1 to the reference fuel. Test Number: IF-XUD9-003 Fuel Code: RF93-T-095 Additive Code: No additive Treat Rate: N/A

Test Number: IF-XUD9-004

Fuel Code: RF93-T-095 Additive Code: Sample D1 Treat Rate: 1 PART in 600

Clean = flows at start of test IF-XUD9-003 Cleaned up = flows at end of test IF-XUD9-004 Test Number: IF-XU D9-005 Fuel Code: RF93-T-095 Additive Code: Sample D1 Treat Rate: 1 PART in 600

Clean = flows at start of test 1F-XUD9-003 Cleaned up = flows at end of test IF-XUD9-005 Summary of Test Results of Example 2:

% Nozzle fouling after Test Cycle 1 , IF-XUD9-003 90% % Nozzle fouling after Test Cycle 2, 1F-XUD9-004 85% % Nozzle fouling after Test Cycle 3, IF-XUD9-005 86% Conclusions:

1) The addition of Sample D1 at a dose rate of 1 :600 vol/vol to reference diesel fuel does not increase the fuel propensity for injector nozzle deposit formation.

2) The results indicated that addition of Sample D1 at a dose rate of 1:600 vol/vol to reference fuel may cause a reduction in existing deposits. Reduction in deposits appeared to stabilise after one test cycle with Sample D1 use.

EXAMPLE 3

I. Trial Background

For three months 40 buses received an appropriate dosage of IFT additive sample D1. For each bus the daily mileage and gallons refuelled was used as data to calculate the daily fuel economy. This was accomplished by calculating the difference in miles driven then dividing that number by the gallons fuelled. The data used in this trial was taken directly from the fuel sheets recorded by re-fuelers.

To establish a pre-additive baseline fuel economy for each bus, mileage and gallons fuelled were calculated for three months prior to additisation. Once the additive was introduced into the buses, we employed the same methods to collect mileage and gallons fuelled data for three months to establish a post-additive fuel economy.

II. Population Characteristics

40 buses participated in the trial. Each engine make and model within the trial population is listed below:

7 International Engines 2 - 1994 engines 4 - 1995 engines 1 - 1996 engine 33 - Caterpillar Engines 0 - 1994 engines 28 - 1995 engines 5 - 1996 engines. In addition, 4 AE vans (all 1995 Chevy engines) participated in the trial and achieved an average of 7.75% fuel economy improvement.

III. Refueling Schedule

Buses were refuelled every other day and broken into two groups - Day and Night shift. To work within this re-fuelling schedule, we categorised the buses participating in the trial into the same four groups: Day 1 , Night 1 and Day 2, Night 2. 4 buses participating in the programme were Day 1 buses; 7 were Day 2 buses. 24 buses participating in the programme were Night 1 buses, 5 buses were Night 2 buses. These buses were selected for us at random.

Our goal was to make sure that each bus received its dose of additive before it received its diesel for the day. Once the additive was added to the tank, the^'impact of the diesel entering the tank on top of the additive would cause the two to splash blend together. Therefore, it was necessary to additise buses every day to ensure that the Day 1 and Night 1 buses received additive on the appropriate re-fuelling day and the Day 2 and Night 2 received additive on the appropriate day.

Dosage for each bus was determined using the ratio of 1 gallon additive to 575 gallons diesel. Based on averages calculated for each bus from the three months prior to additisation, any bus that re-fuelled an average of 20 gallons or less received 400 ml of additive. Any bus that on average, re-fuelled between 21 and 30 gallons received 500 ml of additive. Any bus that on average, refuelled between 31 and 40 gallons received 600 ml of additive.

The additive was introduced into each bus the same way. A plastic tube was slightly inserted into the gas tank, the appropriate dosage of additive was measured in a standard, 2 cup (500 ml) measuring cup and with the help of a funnel, the additive was poured down the tube and entered the tank.

IV. Range of Data

The per cent increase in fuel economy ranged from 27.78% (bus # 505202) to 0.45% (bus # 50680). The range of data can be explained by a number of factors that may have impacted the fuel economy of the bus, or the integrity of the data collection process. The factors listed below were beyond control in this trial: Factors that might affect fuel economy:

• Change in Bus Route: (charter in addition to daily route)

• Change in Number of Stop/Starts within Route (traffic, construction, etc.)

• Change of Bus Driver

• Change in Weather

• Change in Tire Pressure

• Frequency of Oil Change

• Maintenance Problems and Repairs

• Buses not Available for Additisation.

Factors that might affect data collection and create the appearance of a change in fuel economy:

• Lack of Data due to bus re-fuelled at other location

• Lack of Data due to bus re-fuelled out of schedule

• Lack of Data due to re-fueller failing to record data

• Change in re-fueller, or re-fueller habits

• Data recording error made by re-fueller.

For every bus there were a certain number of outliers: data points that appeared not to make sense. These points were either extremely high or extremely low when compared to the entire data set. In order to make sure the data used in the calculation of average fuel economy was statistically significant and not skewed by outliers, the "bell curve" method was applied.

The bell curve is a fundamental principle of statistics which allows use of the data that falls within the normal distribution for each specific bus and filters the outliers that skew the data. For each bus the average miles driven was calculated. Because recording the miles driven for each bus each day was a standard procedure and did not require the re-fueller to remember the additional step of re-setting the fuel meter, we felt that this number had the least chance of being recorded incorrectly. The miles driven was also the variable least likely to be affected by the additive. Assuming that the additive was to have some effect on fuel economy, the miles driven would stay the same since the driving route would not change. The number of gallons fuelled however, might increase or decrease as a result of the additive.

The standard deviation or the measurement of how far the data ranges from the average was calculated based upon the average miles driven. The standard deviation for each bus was then added and subtracted from the average miles driven to create a range of data points that fell within each bus's normal distribution. It is the points within this range that have been used to calculate the post additive average fuel economy.

The only data points for fuel economy that were used for bus 50689 were those whose miles driven ranged between 111 and 189.

Bell Curve Example: Bus # 50689

Average Miles Driven: 150

Standard Deviation: 39

Range: 189 (150 + 39) to 111 (150 - 39).

It should be noted here that the data has been presented in two ways: filtered and unfiltered. The filtered data represents the statistically significant data that was filtered by taking the range of numbers within one standard deviation from the average. The unfiltered data represents the average taken from all of the numbers recorded, whether they were statistically significant or not.

V. Summary of Results

The 40 buses that participated in this trial saw on average, a 10.13% increase in fuel economy. The graph in Figure 1 illustrates this fuel economy improvement, when compared to the baseline miles per gallon.

The range in fuel economy improvements is surprising considering all of the buses operate independently from each other and are independently subject to various factors that influence fuel economy. Therefore, the fuel economy of one bus has no effect on the fuel economy of another bus. These factors have been listed above. It is important to note however, the length of the trial ensured that any factor that would have affected fuel economy, would have had to affect fuel economy for three months consistently in order to be considered a significant variable. None of the factors listed above were a consistent variable for three months and therefore, did not significantly affect the trial. SAVINGS ANALYSIS

Scenario 1 Scenario 2

Assumptions (7%) (10%)

Number of Buses 560 560

Weekly Fuel consumption per bus 60 60

Number of weeks in operation 45 45

Annual Diesel Consumption (in Gallons) 1.512,000 1.512,000

Cost of one gallon of diesel ($) 1.00 1.00 Total Annual Diesel Cost ($) 1.512,000 1.512,000

Additive Cost

Dosage: 1 : 575

Cost per gallon ($) 0.02 0.02

Annual Diesel Consumption (in Gallons) 1 ,512,000 1.512.000

Annual Additive Cost ($) 30,240 30,240

Annual Savings

Fuel Economy Improvement 7% 10% Current Annual Diesel Cost ($) 1,512,000 1 ,512,000 Reduction in Annual Diesel Cost ($) -105,840 -151.200 New Annual Diesel Cost ($) 1,406,160 1 ,360,800 Annual Additive Cost ($) 30,240 30.240 New Total Cost ($) 1.436.400 1.391.040

Annual cost savings 75,600 120,960

Savings per Gallon ($) 0.050 0.080

AVERAGE FOR ALL BUSES/VANS COMPARISON

Additised

Miles/Gallon Miles/Gallon Chanqe

Buses Total Buses 4.9307 5.4300 10.13%

City 4.9381 5.4409 10.18% Highway 4.9258 5.4227 10.09% vans Toiai vans δ.2ϊ36 7.75%

City 7.4916 8.1463 8.74% Highway 8.0176 8.4157 4.97% EXAMPLE 4

Subject: Field Trial of Sample D1 in Rail Road Locomotives

Preamble:

The following study was conducted by measuring one output of two processes, determining their stability to one another and inserting one controlled variable to each process and measuring the output.

Scope:

The scope of this example was to define the structure, limits and statistically evaluate the influence of Sample D1 additive on the performance and efficiency of 2000 and 3000 horsepower locomotives in the field.

Background:

A protocol was established to evaluate the additive utilising one set of General Purpose 38 engines and one set of Special Duty 40 engines with the following statistics:

SD38 Data - General Motors Electro-Motive Division

Horsepower: 2000

No. of Cylinders 16

Cylinder Arrangement 45 "V"

Cylinder Bore and Stroke 9 1/16" x 10"

Total Displacement 10,320 in3 (169 litres)

Operating Principle: 2 Stroke cycle, blower aspirated, unit fuel injection, water cooled cylinder and liners, oil cooled pistons, isochronous speed governor

Full Throttle 900 RPM

Idle Speed 315 PPM.

SD40 - 2 Data - General Motors Electro-Motive Division

Horsepower: 3000

No. of Cylinders 16

Cylinder Arrangement 45 "V"

Cylinder Bore and Stroke 9 1/16" x 10"

Total Displacement 10,320 in3 (169 litres) Operating Principle: 2 stroke cycle, blower aspirated turbo charged, unit fuel injection, water cooled cylinder and liners, oil cooled pistons, isochronous speed governor.

Full Throttle 904 RPM

Idle Speed 318 PPM.

Rationale:

In theory, locomotive engines can be coupled electronically such that both engines respond identically to command control from either engine's control consol. With two theoretically identical engines operating in tandem, we have a platform base which can be subjected to comparison analysis.

Typical Protocol for Coupled Engines A & B

Phase 0 - Fill both engines and mark full point on each engines fuel tank sight glass. Monitor fuel consumed by each engine for a duration of time sufficient to have required a minimum of 3 re-fuelling events without exceptions to establish a base line. Record and establish the per cent of fuel (positive or negative) used by Engine A compared to Engine B, called ΔC. This is the baseline. Phase 0 should only be exited when a stable base line is established without exceptions.

Phase 1 - Select the engine with the highest fuel consumption as compared to its coupled twin and introduce the additive by adjusting a full tank of fuel to a 600:1 fuel to additive ratio. Continue to monitor fuel consumed at re-fuelling by filling to the marked sight gage point. Adjust additive concentration in the selected engine according to the quantity of fuel used to maintain the 600:1 ratio. Record and establish the per cent of fuel (positive or negative) used by Engine A compared to Engine B (ΔC) beginning with the first re-fuel after introduction of the additive to the selected engine. Phase 1 should only be exited after a minimum of 3 to 5 re-fuellings or a stable relationship is seen in the ΔC. Stability in this case is defined as less than a 1 % change in the ΔC from one re-fuel to the next (see Analysis Section). Phase 2 - Introduce the second twin engine to the additive by adjusting a full tank of fuel to the 600:1 ratio. Continue monitoring fuel consumed in the same manner as Phase 1. Record and establish the per cent of fuel (positive or negative) used by Engine A compared to Engine B (ΔC) beginning with the first re-fuel after introduction of the additive to the second engine. The same rationale is used in exiting Phase 2 as was used in Phase 1.

Phase 3 - Remove the additive from the engine selected in Phase 1. Continue monitoring fuel consumed in the same manner as Phases 1 and 2. Record and establish the per cent of fuel (positive or negative) used by Engine A compared to Engine B (ΔC) beginning with the first re-fuel after stopping the additive in the first engine selected in Phase 1 engine. It will be necessary to calculate the residual diluted concentration in the tank at each re-fuel after having withdrawn the additive from the engine selected in Phase 1. The criterion for exiting Phase 3 is only after witnessing a gradual shift in relationships between the two engines and then a period of stability where they no longer exhibit a shift. This phase has the dual purpose of demonstrating that a shift will occur when the additive is removed and to estimate how long the residual benefit exists from the additive.

Phase 4 - Remove the additive from the engine selected in Phase 2. Monitor fuel usage on both engines with neither engine having the additive. Record and establish the per cent of fuel (positive or negative) used by Engine A compared to Engine B (ΔC) beginning with the first re-fuel after removal of the additive to the second engine. Termination of this phase and concluding the test would be similar to Phase 3.

Protocol Test Results:

Locomotive ID #'s 43 & 44

Type of work Long haul coal train up to 65 - 132 gross ton cars

Number of re-fuellings 29

Number of exceptions^* (data n/a) 6

Phase 0 ΔC = 6.87% (44 using more fuel than 43)

Phase 1 ΔC = -6.37% (Engine 44 selected for Phase 1 - a 13.24% improvement in Engine 44's performance compared to

Engine 43) Phase 2 ΔC = -1.54% (Engine 43's performance improved by 4.83% compared to Engine 44 which is also receiving the additive)

Phase 3 ΔC = 0.02% (Engine 44 loses 1.56% in performance after having the additive withdrawn. Residual benefit of the additive has not been determined.

Phase 4 ΔC = -4.28% (When additive withdrawn from both engines, Engine 43 now using more than engine 44)

Locomotive ID #'s 179 & 180 Type of work Miscellaneous short haul freight of up to 40 - gross ton cars and rail yard switching

Number of re-fuellings In progress Phase 0 ΔC = -0.94% (Engine 179 using more fuel than Engine 180) Phase 1 ΔC = 6.06% (Engine 179 selected for Phase 1 - a 7% improvement in Engine 179's performance compared to Engine 180)

Phase 2 ΔC = In progress

Conclusions:

> The addition of Sample D1 additive to the 3000 horsepower locomotive engine number 44 resulted in a 13% improvement in fuel efficiency compared to its twin engine number 43. These two engines were working a longer haul coal car assignment.

> When introduction of the Sample D1 additive is made to the 2000 horsepower engine number 179 working primarily an inefficient switching assignment, the result was a 7% improvement in fuel efficiency compared to its twin engine number 180. > As the Sample D1 additive was introduced to engine 43 after having been introduced to engine 44, there was a 4.83% improvement in engine 43's performance compared to engine 44. Keeping in mind that the comparison numbers are derived from two now "clean" engines, we do not expect the shift to be as pronounced as it was when one engine is "clean" and the other "dirty".

Although not subjected to performance testing herein, the following blended additive admixtures in Table 1 were formulated and dissolved into hydrocarbon fuel.

TABLE 1 :

Claims

1. A fuel composition consisting of at least 95% by weight of predominantly or entirely hydrocarbon liquid fuel and 0.001 to 5.0% by weight of fuel additive, wherein the additive consists of:

a) 20 to 90% by weight of at least one alkoxylated alcohol corresponding to Formula

(0

R²

R¹-O-(-CHCH₂O-)χ-H (I) wherein

-R² is H or CH₃, and -x is 1 - 7;

(b) 40 to 10% by weight of at least one polyalkylene glycol ester corresponding to the following general Formula (II)

O R⁴

R³-C-0 -(-CHCH₂O-K-R⁵ (II) wherein -R is Cii-C-|₉, -R⁴ is H or CH₃, -y is 1 - 20, -R⁵ is H or COR³; and

(c) 40 to 0% by weight of at least one alkanolamide corresponding to the following general Formula (III) O CH₂CH₂OH

/

R⁶-C-N

R⁷ (III)

wherein

-R⁷ is H or CH₂CH₂OH

provided that the sum of (a), (b) and, when present (c), constitutes 100% by weight of said fuel additive present in the fuel composition.

2. A composition as claimed in Claim 1 , wherein alkoxylated alcohol (a) comprises 20 to 70% by weight of the additive, preferably 40 to 60% by weight, more preferably 50 to 60% by weight

3. A composition as claimed in either preceding Claim, wherein R¹ is C₉-C₁₁ and x is about 2.5.

4. A composition as claimed in any preceding Claim, wherein polyalkylene glycol ester (b) comprises 40 to 15% by weight of the additive, preferably 35 to 25% by weight, more preferably 30 to 25% by weight.

5. A composition as claimed in any preceding Claim, wherein R³ is C₁₇ and R⁵ is COR³.

6. A composition as claimed in any preceding Claim, wherein alkanolamide (c) when present comprises 40 to 15% by weight of the additive, preferably 25 to 15% by weight.

7. A composition as claimed in any preceding Claim, wherein R⁶ is C₁₇ and R⁷ is CH₂CH₂OH.

8. A composition as claimed in any preceding Claim, wherein the liquid hydrocarbon fuel is naturally obtained petroleum distillate fuel or residual fuel oil such as diesel fuel, gasoline or kerosene, optionally blended with other alternative predominantly hydrocarbon fuel.

9. A composition as claimed in Claim 8, wherein the fuel is gasoline optionally blended with gas-to-liquid condensate and/or alkanol such as ethanol.

10. A composition as claimed in Claim 8, wherein the fuel is kerosene optionally blended with any predominantly hydrocarbon based alternative thereto.

11. A composition as claimed in Claim 8, wherein the fuel is diesel optionally blended with biodiesel, gas-to-liquid diesel condensates, and diesel/alkanol such as diesel/ethanol blends.

12. A composition as claimed in Claim 8, wherein the fuel comprises of residual heavy fuel oil.

13. A fuel additive concentrate which essentially consists of about 80 - 20% by weight of a fuel additive consisting of (a) plus (b) optionally plus (c) as defined in Claim 1 and about 20 to 80% of fuel solvent.

14. A concentrate as claimed in Claim 13, wherein the fuel additive comprises about 70 to 30% by weight of the concentrate and the fuel solvent comprises about 30 to 70% by weight of the concentrate.

15. A concentrate as claimed in Claim 13, wherein the fuel additive comprises about 60 to 40% by weight of the concentrate and the fuel solvent comprises about 40 to 60% by weight of the concentrate.

16. A concentrate as claimed in any one of Claims 13 to 15, wherein the solvent is a fuel selected from petroleum distillate fuel and/or alternative diesel, gasoline and kerosene fuels.

17. A fuel composition formulated to produce improved fuel economy when subject to combustion, said composition comprising: about 95 to 99.9999% by weight of predominantly hydrocarbon liquid fuel; and about 0.0001 to 5% by weight of fuel additive concentrate as defined in any one of Claims 13 to 16.

18. A method of making a fuel additive suitable for use in a composition as claimed in any one of Claims 1 to 12, the method comprising, the steps of admixing in any order a blend consisting of the following components: a) 20 to 90% by weight of at least one alkoxylated alcohol having the following general Formula (I)

R²

R¹ -O -(-CHCH₂O-)_X-H (I) wherein

-R² is H or CH₃, and

-x is 1 - 7;

O R⁴

R³-C-0 -(-CHCH₂O -)_y-R⁵ (II) wherein

-R⁴ is H or CH₃,

-y is 1 - 20,

-R⁵ is H or COR³; and

optionally

(c) 40 to 0% by weight of at least one alkanolamide corresponding to the following general Formula (III)

O CH₂CH₂OH u / R⁶-C-N \ R⁷ (III)

wherein

-R⁷ is H or CH₂CH₂OH;

subject to the proviso that the sum of the amounts of components (a), (b) and, when present, (c) equates to 100% by weight of said fuel additive.

19. A method as claimed in Claim 18, wherein the step of preparing the blend comprises admixing about 20 to 70% by weight, preferably 40 to 60%, more preferably 50 to 60% of alkoxylated alcohol (a).

20. A method as claimed in Claim 18 or 19, wherein R¹ is Cg-C₁₁ and x is about 2.5.

21. A method as claimed in any of Claims 18 to 20, wherein the step of preparing the blend comprises admixing 40 to 15% by weight, preferably 35 to 25%, more preferably 30 to 25% by weight of polyalkylene glycol ester (b).

22. A method as claimed in any one of Claims 18 to 21 , wherein R³ is Ci₇ and R⁵ is COR³.

23. A method as claimed in any one of Claims 18 to 22, wherein the step of preparing the blend comprises admixing 40 to 15% by weight, preferably 25 to 15% by weight of alkanolamide (c).

24. A method as claimed in any one of Claims 18 to 23, wherein R⁶ is about C₁₇ and R⁷ is - CH₂CH₂OH.

25. A method of making a fuel additive concentrate comprising, in any order, the steps of:

-preparing an additive blend comprising the steps of any one of Claims 18 to 24, in any order;

-admixing about 80 to 20% by weight of the additive blend with about 20 to 80% by weight of predominantly or entirely hydrocarbon fuel solvent.

26. A method as claimed in Claim 25, wherein the solvent is a fuel selected from one or more of petroleum distillate derived diesel, gasoline and kerosene, optionally blended with alternative non petroleum distillate derived predominantly hydrocarbon fuel.

27. A method as claimed in Claim 25 or 26, wherein the step of preparing the concentrate comprises the step of admixing about 70 to 30% by weight of the additive blend with about 30 to 70% by weight of the solvent.

28. A method as claimed in Claim 27, wherein the step of preparing the concentrate comprises the step of admixing about 60 to 40% by weight of the additive blend with about 40 to 60% by weight of the solvent.

29. A method of making a fuel composition formulated to improve fuel economy when subject to combustion, said method comprising the steps of:

preparing a fuel additive concentrate according to a method as claimed in any one of Claims 25 to 28; admixing about 95 to 99.999% by weight of predominantly hydrocarbon liquid fuel with 0.0001 to 5% by weight of said fuel additive concentrate.

30. A method as claimed in Claim 29, wherein the solvent comprises fuel selected from petroleum distillate derived diesel, gasoline and kerosene, optionally blended with alternative non petroleum distillate derived predominantly hydrocarbon fuel.