# Patent

## Title
Fuel blends

## Abstract

There is provided a diesel fuel blend comprising one or more commercially available diesel fuels; ethanol and a coupling agent.

## Background
FIELD OF THE INVENTION
The invention relates to fuel blend compositions including diesel fuel and alcohol.
BACKGROUND OF THE INVENTION
In this specification, where a document, act or item of knowledge is referred to or discussed, this reference or discussion is not to be taken as an admission that the document, act or item of knowledge or any combination thereof was at the priority date:

    
    
        (a) part of common general knowledge; or
        (b) known to be relevant to an attempt to solve any problem with which this specification is concerned.
    
    


Diesel oil, due to its cost and availability, continues to be the backbone for industry around the world being the principal fuel for use in truck, ships, trains, some cars and other automotive equipment and different stationary types of engines.
It is recognised that the combustion of diesel fuel in engines can be hazardous to the environment. In particular, the partial combustion of diesel fuel to carbon-based particulates, hydrocarbons and carbon monoxide creates noxious black exhaust gases while the additional problem of nitrogen oxide production adds to the pollution. This is particularly observable in trucks and other automotive vehicles where noxious black exhaust gases can be seen as they are released from the vehicle exhaust into the environment.
Attempts have been made over the years to address the environmental concerns associated with exhaust fumes from engines by using alcohols such as methanol or ethanol as fuels. Such attempts, for instance, have established that 15% ethanol and 85% diesel oil provides a fuel of acceptable burning capacity without the necessity of modifying existing diesel engines.
The problem with using ethanol or methanol as a fuel in conjunction with diesel oil is that ethanol and methanol are immiscible with diesel oil within the normal range of operating temperatures, that is, they cannot be uniformly mixed or blended into one phase without rapid separation into their component parts.
One attempt to address the immiscibility problem involved mixing diesel fuel, a C3 (excluding n-propanol)-C22 organic alcohol and either (i) ethanol and/or n-propanol or (ii) a mixture of two or more of methanol, ethanol and n-propanol. Another attempt tried mixing diesel fuel, up to 20% ethanol or n-propanol and up to 15% of a fatty acid and/or organic ester.
However the presence of a significant water content may cause separation of the alcohol and diesel fuel. Water can enter into the fuel in a number of ways. These include (i) absorbing water from the air, (ii) the alcohol often having some intrinsic water content, and (iii) diesel fuel picking up water from the refinery pipes which are usually flushed with water.
Water also forms a constant boiling azeotrope with ethanol. Further attempts to remove the water fail by distillation. Even if substantially dehydrated ethanol is prepared, it is very hygroscopic and will quickly absorb moisture from the atmosphere unless subjected to special storage techniques.
One attempt to address the water content problem involved the use of a surfactant system comprising N, N-dimethylamine and a long chain fatty acid substance in a hybrid fuel microemulsion containing diesel fuel, water and alcohol. These trials further concluded that the advantage provided by N,N-dimethylamine could not be extrapolated to all amine compounds because in a comparative trial 2-amino-2-methyl-1-propanol was substituted for N,N-dimethylamine and the substituted formulations were not water tolerant to the same low temperatures.
A second attempt involved using an ethoxylated fatty alcohol and/or its reaction product with an amide as a stabilising additive. A third attempt involves using a polymeric fuel additive formed by reacting together an ethoxylated alcohol and a fatty alkanolamide.
There is therefore a need for fuel blends which are more water tolerant, especially at lower temperatures.
SUMMARY OF THE INVENTION
It has been found that diesel fuel and ethanol blends may be prepared which are more water tolerant.
According to a first aspect of the invention there is provided a diesel fuel blend comprising:

    
    
        (a) greater than about 65% of one or more diesel fuels;
        (b) up to about 20% v/v of ethanol; and
        (c) up to about 15% v/v of a coupling agent comprising:
        
            (i) greater than about 60% w/w 2-ethylhexanol (also called iso-octanol);
            (ii) from 10 to 40% w/w of one or more fatty alkanolamides; and
            (iii) up to about 10% w/w of one or more fatty acids.
        
        
    
    


The diesel fuel suitable for use in this invention is any essentially petroleum-based fuel which is suitable for use in a diesel engine.
The sources of ethanol to be used in the invention may range from commercially available rectified spirit which typically has 5% water through to absolute ethanol. More preferably, the ethanol will be super dry having less then 0.2% water.
Those skilled in the art will be aware of suitable fatty alkanolamides which may be used. The fatty alkanolamide may be derived from primary or secondary alkanolamines. Examples of suitable alkanolamines include ethanolamine, diethanolamine, diglycolamine, isopropanolamine and diisopropanolamine. The fatty acid portion is preferably selected from the C8 to C20 saturated or unsaturated fatty acids and may be derived from natural vegetable origins (e.g. coconut, canola, soybean), animal origins (e.g. tallow or lard) or synthetic origins. Preferably, the fatty alkanolamide is oleyl diethanolamide or coconut diethanolamide.
Those skilled in the art will be aware of suitable fatty acids which may be used. The fatty acid is preferably selected from the C8 to C20 saturated or unsaturated fatty acids and may be derived from natural vegetable origins (e.g. coconut, canola, soybean), animal origins (e.g. tallow or lard) or synthetic origins. Preferably the fatty acid is commercially available oleic acid or low rosin tall oil.
According to a second aspect of the invention, there is provided a coupling agent for use in fuel blends comprising diesel fuel and ethanol, the coupling agent comprising:

    
    
        (i) greater than about 60% w/w 2-ethylhexanol (also called iso-octanol);
        (ii) from 10 to 40% w/w of one or more fatty alkanolamides; and
        (iii) up to about 10% w/w of one or more fatty acids.
    
    


It has further been found that alternative diesel fuel and ethanol blends may be prepared which are more water tolerant.
According to a third aspect of the invention there is provided a diesel fuel blend comprising:

    
    
        (a) greater than about 65% v/v of one or more diesel fuels;
        (b) up to about 20% v/v of ethanol; and
        (c) up to about 15% of a coupling agent comprising:
        
            (i) greater than about 60% w/w of one or more alkyl esters of fatty acids;
            (ii) from 10 to 40% w/w of one or more fatty alkanolamides; and (iii) up to about 10% w/w of one or more fatty acids.
        
        
    
    


Those skilled in the art will be aware of suitable alkyl esters of fatty acids which may be used. The fatty acid portion is preferably selected from the C8 to C20 saturated or unsaturated fatty acids and may be derived from natural vegetable origins (e.g. coconut, canola, soybean), animal origins (e.g. tallow or lard) or synthetic origins. The alkyl esters may be derived from C1 to C8 alcohols. Preferably, the alkyl ester of fatty acids is methyl soyate or methyl canolate.
According to a fourth aspect of the invention, there is provided a coupling agent for use in fuel blends comprising diesel fuel and ethanol, the coupling agent comprising:

    
    
        (i) greater than about 60%/% w/w of one or more alkyl esters of fatty acids;
        (ii) from 10 to 40% w/w of one or more fatty alkanolamides; and
        (iii) up to about 10% w/w of one or more fatty acids.
    
    


Further it has been found that the two alternative formulations may be combined to provide alternative diesel fuel and ethanol blends may be prepared which are more water tolerant.
According to a fifth aspect of the invention there is provided a diesel fuel blend comprising:

    
    
        (a) greater than about 65% v/v of one or more diesel fuels;
        (b) up to about 20% v/v of ethanol; and
        (c) up to about 15% of a coupling agent comprising:
        
            (i) greater than about 60% w/w of one or more alkyl esters of fatty acids and/or 2-ethylhexanol (also called iso-octanol);
            (ii) from 10 to 40% w/w of one or more fatty alkanolamides; and
            (iii) up to about 10% w/w of one or more fatty acids.
        
        
    
    




EXAMPLES
The invention will now be further explained and illustrated by reference to the following non-limiting examples.
Components
The following components are used in the formulations in the examples below.
















2-ethylhexanol
Ex Orica, Australia



Butyl canolate
Ex Victorian Chemical Company, Australia



Ethanol
Anhydrous ethanol ex CSR, Australia



Ethyl tallowate
Ex Victorian Chemical Company, Australia



Isooctyl oleate
Ex Clariant, Australia



Kerosene
Kerosene blue ex Recochem, USA



Methyl canolate
Ex Victorian Chemical Company, Australia



Methyl cocoate
Ex Victorian Chemical Company, Australia



Methyl soyate
Ex BF Goodrich, USA or P&G, USA



Oleic acid
Ex Dragon Chemicals, Australia



P878 mineral oil
Ex Shell Oil, Australia



USA Diesel
Winter grade ex Exxon, USA



Vicamid 825
Oleyl diethanolamide ex Victorian Chemical




Company, Australia



Vicamid 528
Coco diethanolamide ex Victorian Chemical




Company, Australia










Example 1
A coupling agent according to the second aspect of the invention was prepared as follows:














Component
Amount (% w/w)



















2-ethylhexanol
80



Vicamid 825
17



Oleic acid
3










The 2% v/v coupling agent was combined with 90% v/v diesel fuel and 8% v/v ethanol to provide a fuel blend according to the first aspect of the invention. This fuel blend was tested in two Landcruiser 4WD utility vehicles and one light diesel truck and the engines ran satisfactorily.
Example 2
A blend of ethanol and coupling agent was prepared according to the fourth aspect of the invention as follows:














Component
Amount (% w/w)



















Ethanol
63.7



Methyl soyate
27.5



Vicamid 825
8.0



Oleic acid
0.8










10% v/v of the ethanol blend was combined with 90% v/v diesel fuel to provide a fuel blend according to the third aspect of the invention. Similarly, 15% v/v of the ethanol blend was combined with 85% v/v diesel fuel to provide a fuel blend which satisfactorily ran the diesel (4 cylinder 1.5 liter) engine of a Volkswagen “Golf”.
Example 3
Fuel blends according to the third aspect of the invention were prepared and tested for water stability.














Component
3A (ml)
3B (ml)





Kerosene
150
150


P878 mineral oil
150
150


USA Diesel
400
500


Methyl Soyate
180
100


Ethanol
100
80


Vicamid 825
18 g
18 g


Oleic acid
 2 g
 2 g





Water stability testing
Formulation 1
Formulation 2





Overnight in freezer @ −8° C.
clear uniform
clear uniform


0.5 g water added, 2 hours in
clear uniform
clear uniform


freezer at −8° C.


Further 0.5 g water added, 2
clear uniform
2 layers, cloudy


hours in freezer at −8° C.


Cloud point of wet product*
<−8° C.
+5° C.


Final water content** (%)
0.19
0.19





*The appearance of the cloud point shows the temperature at which instability of the formulation occurs. The lower the temperature of the cloud point evidences greater stability. The cloud point has no relevance to engine performance.


**Water content in the formulations, as here and later mentioned through the patent, has been measured via the Karl Fischer titration method (D4377 of the ASTM).






These results show that by the addition of the additives the water tolerance of the formulation has been improved.
Example 4
A series of formulations of 20% v/v anhydrous alcohol in USA ‘winter grade’ diesel oil were prepared and water stability compared.

















Formulation
Control
4A
4B
4C






















diesel
80
65
65
65



ethanol
20
20
20
20



2-ethylhexanol
—
9
—
—



methyl cocoate
—
—
9
—



methyl soyate
—
—
—
9



Vicamid 825
—
5.5
5.5
5.5



Oleic acid
—
0.5
0.5
0.5
























Water stability
Control
4A
4B
4C



















Initial water (%)
0.11
0.09
0.10
0.10


Initial cloud point (CP) (° C.)
+12
<−8
<−8
<−8


+0.1% water, CP
n/a
<−8
<−8
<−8


Further +0.1% water, CP
n/a
<−8
<−8
−6


Further +0.1% water, CP
n/a
<−8
<−8
−3


Further +0.1% water, CP
n/a
<−8
−5
+2


Further +0.1% water, CP
n/a
<−8
0
n/a


Further +0.1% water, CP
n/a
<−8
+6
n/a


Further +1.0% water, CP
n/a
<−8
n/a
n/a


Further +0.2% water, CP
n/a
−4
n/a
n/a


Further +0.1% water, CP
n/a
+2
n/a
n/a


Final water (%)
0.11
2.11
0.81
0.58









These results further show that by the addition of the additives the water tolerance of the formulation has been improved. Indeed formulation 4A is sufficiently robust that those skilled in the art will recognise that rectified ethanol can be used.
Example 5
A series of formulations of 10% v/v anhydrous alcohol in USA ‘winter grade’ diesel oil were prepared and water stability compared.


















Formulation
Control
5A
5B
5C
5D























Diesel
90
80
80
80
80



Ethanol
10
10
10
10
10



2-ethylhexanol
—
6
—
—
—



Methyl soyate
—
—
6
—
—



Butyl canolate
—
—
—
6
—



Ethyl tallowate
—
—
—
—
6



Vicamid 825
—
3.6
3.6
3.6
3.6



Oleic acid
—
0.4
0.4
0.4
0.4

























Water stability
Control
5A
5B
5C
5D




















Initial water (%)
0.07
0.07
0.07
0.07
0.07


Initial cloud point (CP) (° C.)
+2
<−8
<−8
<−8
<−8


+0.1% water, CP
n/a
<−8
<−8
<−8
<−8


Further +0.1% water, CP
n/a
<−8
+7
+11
+7


Further +0.1% water, CP
n/a
<−8
n/a
n/a
n/a


Further +0.1% water, CP
n/a
<−8
n/a
n/a
n/a


Further +0.3% water, CP
n/a
<−8
n/a
n/a
n/a


Further +0.1% water, CP
n/a
+4
n/a
n/a
n/a


Final water (%)
0.07
1.01
0.30
0.30
0.29









These results further show that by the addition of the additives the water tolerance of the formulation has been improved. Indeed formulation 5A is sufficiently robust that those skilled in the art will recognise that rectified ethanol can be used.
Example 6
A series of formulations of 5% v/v anhydrous alcohol in USA ‘winter grade’ diesel oil were prepared and water stability compared.


















Formulation
Control
6A
6B
6C
6D























Diesel
95
90
90
90
90



Ethanol
5
5
5
5
5



2-ethylhexanol
—
3
—
—
—



Isooctyl oleate
—
—
3
—
—



Methyl soyate
—
—
—
3
—



Butyl canolate
—
—
—
—
3



Vicamid 825
—
1.8
1.8
1.8
1.8



Oleic acid
—
0.2
0.2
0.2
0.2

























Water stability
Control
6A
6B
6C
6D




















Initial water (%)
0.04
0.04
0.04
0.04
0.04


Initial cloud point (CP) (° C.)
<−8
<−8
<−8
<−8
<−8


+0.1% water, CP
+37
<−8
+33
+25
+26


Further +0.1% water, CP
n/a
<−8
n/a
n/a
n/a


Further +0.1% water, CP
n/a
−6
n/a
n/a
n/a


Further +0.1% water, CP
n/a
+28
n/a
n/a
n/a


Final water (%)
0.16
0.39
0.16
0.16
0.16









These results further show that by the addition of the additives the water tolerance of the formulation has been improved.
Example 7
A series of formulations of 10% v/v anhydrous alcohol in USA ‘winter grade’ diesel oil were prepared using coco diethanolamide and water stability compared.

















Formulation
Control
7A
7B
7C






















Diesel
90
80
80
80



Ethanol
10
10
10
10



Methyl soyate
—
6
6
6



Vicamid 528
—
3.6
3.3
3.0



Oleic acid
—
0.4
0.7
1.0
























Water stability
Control
7A
7B
7C



















Initial water (%)
0.07
0.05
0.06
0.06


Initial cloud point (CP) (° C.)
+2
−5
<−8
<−8


+0.1% water, CP
n/a
+11
−1
<−8


Further +0.1% water, CP
n/a
n/a
n/a
+16


Further +0.1% water, CP
n/a
n/a
n/a
n/a


Final water (%)
0.07
0.17
0.17
0.39









These results further show that by the addition of the additives the water tolerance of the formulation has been improved.
Example 8
A formulation of 10% v/v anhydrous alcohol in USA ‘winter grade’ diesel oil was prepared using methyl canolate and water stability compared.















Formulation
Control
8A




















Diesel
90
80



Ethanol
10
10



Methyl canolate
—
6



Vicarmid 825
—
3.6



Oleic acid
—
0.4

























Water stability
Control
8A




















Initial water (%)
0.07
0.06



Initial cloud point (CP) (° C.)
+2
<−8



+0.1% water, CP
n/a
<−8



Further +0.1% water, CP
n/a
+11



Further +0.1% water, CP
n/a
n/a



Final water (%)
0.07
0.37










These results further show that by the addition of the additives the water tolerance of the formulation has been improved.
Example 9
A formulation of 15% v/v anhydrous alcohol in USA ‘winter grade’ diesel oil was prepared using a blend of additives and water stability compared.















Formulation
Control
9A




















Diesel
85
72



Ethanol
15
15



2-Ethylhexanol
—
4



Methyl soyate
—
4



Vicamid 825
—
4.5



Oleic acid
—
0.5

























Water stability
Control
9A




















Initial water (%)
0.09
0.08



Initial cloud point (CP) (° C.)
+6
<−8



+0.1% water, CP
n/a
<−8



Further +0.1% water, CP
n/a
<−8



Further +0.1% water, CP
n/a
<−8



Further +0.1% water, CP
n/a
<−8



Further +0.3% water, CP
n/a
−5



Further +0.1% water, CP
n/a
+6



Final water (%)
0.09
1.01










These results further show that the water tolerance of the formulation has been improved. Indeed formulation 9A is sufficiently robust that those skilled in the art will recognise that rectified ethanol can be used.
The word ‘comprising’ and forms of the word ‘comprising’ as used in this description do not limit the invention claimed to exclude any variants or additions.
Modifications and improvements to the invention will be readily apparent to those skilled in the art. Such modifications and improvements are intended to be within the scope of this invention.

## Claims

1. A diesel fuel blend comprising one or more diesel fuels, ethanol, and a coupling agent, wherein the amounts of the one or more diesel fuels, ethanol and coupling agent in the blend are:
(a) greater than about 65% of the one or more diesel fuels;
(b) up to about 20% v/v of the ethanol; and
(c) up to about 15% v/v of the coupling agent;

wherein ethanol and the coupling agent are present in the blend, and the coupling agent comprises:
(i) greater than about 60% w/w 2-ethylhexanol;
(ii) from 10 to 40% w/w of one or more fatty alkanolamides; and
(iii) up to about 10% w/w of one or more fatty acids;

wherein one or more fatty acids are present in the coupling agent.

2. A diesel fuel blend according to claim 1 wherein the one or more alkanolamides are derived from ethanolamine, diethanolamine, diglycolamine, isopropanolamine and diisopropanolamine.

3. A diesel fuel blend according to claim 1 wherein the one or more alkanolamides are derived from C8 to C20 saturated or unsaturated fatty acids of natural or synthetic origin.

4. A diesel fuel blend according to claim 1 wherein the alkanolamide is oleyl diethanolamide.

5. A diesel fuel blend according to claim 1 wherein the one or more fatty acids are selected from the group consisting of C8 to C20 saturated or unsaturated fatty acids of natural or synthetic origin.

6. A diesel fuel blend according to claim 1 wherein the fatty acid is oleic acid.

7. A coupling agent for use in fuel blends comprising diesel fuel and ethanol, the coupling agent comprising:
(a) greater than about 60% w/w 2-ethylhexanol;
(b) from 10 to 40% w/w of one or more fatty alkanolamides; and
(c) up to about 10% w/w of one or more fatty acids;

wherein one or more fatty acids are Present in the coupling agent.

8. A diesel fuel blend comprising one or more diesel fuels, ethanol, and a coupling agent, wherein the amounts of the one or more diesel fuels, ethanol and coupling agent in the blend are:
(a) greater than about 65% v/v of the one or more diesel fuels;
(b) up to about 20% v/v of the ethanol; and
(c) up to about 15% of the coupling agent;

wherein ethanol and the coupling agent are present in the blend, and the coupling agent comprises:
(i) greater than about 60% w/w of one or more alkyl esters of fatty acids;
(ii) from 10 to 40% w/w of one or more fatty alkanolamides; and
(iii) up to about 10% w/w of one or more fatty acids;

wherein one or more fatty acids are present in the coupling agent.

9. A diesel fuel blend according to claim 8 wherein the one or more alkyl esters of fatty acids are derived from C8 to C20 saturated or unsaturated fatty acids of natural or synthetic origin.

10. A diesel fuel blend according to claim 8 wherein the one or more alkyl esters of fatty acids are derived from C1 to C8 alcohols.

11. A diesel fuel blend according to claim 8 wherein the one or more alkanolamides are derived from ethanolamine, diethanolamine, diglycolamine, isopropanolamine and diisopropanolamine.

12. A diesel fuel blend according to claim 8 wherein the one or more alkanolamides are derived from C8 to C20 saturated or unsaturated fatty acids of natural or synthetic origin.

13. A diesel fuel blend according to claim 8 wherein the alkanolamide is oleyl diethanolamide.

14. A diesel fuel blend according to claim 8 wherein the one or more fatty acids are selected from the group consisting of C8 to C20 saturated or unsaturated fatty acids of natural or synthetic origin.

15. A diesel fuel blend according to claim 8 wherein the fatty acid is oleic acid.

16. A coupling agent for use in fuel blends comprising diesel fuel and ethanol, the coupling agent comprising:
(a) greater than about 60% w/w of one or more alkyl esters of fatty acids;
(b) from 10 to 40% w/w of one or more fatty alkanolamides; and
(c) up to about 10% w/w of one or more fatty acids;

wherein one or more fatty acids are present in the coupling agent.

17. A diesel fuel blend comprising one or more diesel fuels, ethanol, and a coupling agent, wherein the amounts of the one or more diesel fuels, ethanol and coupling agent in the blend are:
(a) greater than about 65% v/v of the one or more diesel fuels;
(b) up to about 20% v/v of the ethanol; and
(c) up to about 15% of the coupling agent;

wherein ethanol and the coupling agent are present in the blend, and the coupling agent comprises:
(i) greater than about 60% w/w of one or more alkyl esters of fatty acids, 2-ethylhexanol, or a combination of one or more of said alkyl esters of fatty acids and 2-ethylhexanol;
(ii) from 10 to 40% w/w of one or more fatty alkanolamides; and
(iii) up to about 10% w/w of one or more fatty acids;

wherein one or more fatty acids are present in the coupling agent.