Canadian Patents Database / Patent 2839237 Summary

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(12) Patent Application: (11) CA 2839237
(54) English Title: COMPOSITION
(54) French Title: COMPOSITION
(51) International Patent Classification (IPC):
  • C10L 1/12 (2006.01)
  • C10L 1/198 (2006.01)
(72) Inventors :
  • NIELSEN, JENS MOGENS (Denmark)
  • DUELUND, MAJA (Denmark)
  • BECH, ALLAN TORBEN (Denmark)
(73) Owners :
  • DUPONT NUTRITION BIOSCIENCES APS (Denmark)
(71) Applicants :
  • DUPONT NUTRITION BIOSCIENCES APS (Denmark)
(74) Agent: TORYS LLP
(74) Associate agent:
(45) Issued:
(86) PCT Filing Date: 2012-06-29
(87) Open to Public Inspection: 2013-01-03
(30) Availability of licence: N/A
(30) Language of filing: English

(30) Application Priority Data:
Application No. Country/Territory Date
1111029.3 United Kingdom 2011-06-29

English Abstract

The present invention provides a fuel composition comprising: (a) a fuel; and (b) a polyglycerol ester of a fatty acid; wherein the polyglycerol composition used to form the polyglycerol ester of a fatty acid comprises a mixture of diglycerol in an amount of 11.0 to 34.0 weight% based on the combined weight of the polyglycerols; triglycerol in an amount of 9.5 to 24.5 weight% based on the combined weight of the polyglycerols; tetraglycerol in an amount of 6.0 to 21.0 weight% based on the combined weight of the polyglycerols; pentaglycerol in an amount of 3.5 to 19.0 weight% based on the combined weight of the polyglycerols; hexaglycerol in an amount of 6.0 to 13.5 weight% based on the combined weight of the polyglycerols; heptaglycerol in an amount of 5.0 to 13.0 weight% based on the combined weight of the polyglycerols; octaglycerol in an amount of 3.0 to 12.0 weight% based on the combined weight of the polyglycerols; nonaglycerol in an amount of 1.5 to 10.0 weight% based on the combined weight of the polyglycerols; decaglycerol in an amount of 0.0 to 8.0 weight% based on the combined weight of the polyglycerols; and unadecaglycerol in an amount of 0.0 to 7.0 weight% based on the combined weight of the polyglycerols.


French Abstract

L'invention concerne une composition de carburant, comprenant : (a) un carburant ; et (b) un ester de polyglycérol d'acide gras. La composition de polyglycérol utilisée pour former l'ester de polyglycérol d'acide gras comprend un mélange de diglycérol à raison de 11,0 à 34,0% en poids sur la base du poids combiné des polyglycérols ; un triglycérol à raison de 9,5 à 24,5% en poids sur la base du poids combiné des polyglycérols ; un tétraglycérol à raison de 6,0 à 21,0% en poids sur la base du poids combiné des polyglycérols ; un pentaglycérol à raison de 3,5 à 19,0% en poids sur la base du poids combiné des polyglycérols ; un héxaglycérol à raison de 6,0 à 13,5% en poids sur la base du poids combiné des polyglycérols ; un heptaglycérol à raison de 5,0 à 13,0% poids sur la base du poids combiné des polyglycérols ; un octaglycérol à raison de 3,0 à 12,0 % en poids sur la base du poids combiné des polyglycérols ; un nonaglycérol à raison de 1,5 à 10,0% en poids sur la base du poids combiné des polyglycérols ; un décaglycérol à raison de 0,0 à 8,0% en poids sur la base du poids combiné des polyglycérols ; et un unadécaglycérol à raison de 0,0 à 7,0 % en poids sur la base du poids combiné des polyglycérols.


Note: Claims are shown in the official language in which they were submitted.


47

CLAIMS

1. A fuel composition comprising:
(a) a fuel; and
(b) a polyglycerol ester of a fatty acid,
wherein the polyglycerol composition used to form the polyglycerol ester of a
fatty acid
comprises a mixture of
diglycerol in an amount of 11.0 to 34.0 weight% based on the combined weight
of
the polyglycerols;
triglycerol in an amount of 9.5 to 24.5 weight% based on the combined weight
of
the polyglycerols,
tetraglycerol in an amount of 6.0 to 21.0 weight% based on the combined weight

of the polyglycerols;
pentaglycerol in an amount of 3.5 to 19.0 weight% based on the combined
weight of the polyglycerols;
hexaglycerol in an amount of 6.0 to 13.5 weight% based on the combined weight
of the polyglycerols,
heptaglycerol in an amount of 5.0 to 13.0 weight% based on the combined
weight of the polyglycerols;
octaglycerol in an amount of 3.0 to 12.0 weight% based on the combined weight
of the polyglycerols,
nonaglycerol in an amount of 1.5 to 10.0 weight% based on the combined weight
of the polyglycerols;
decaglycerol in an amount of 0.0 to 8.0 weight% based on the combined weight
of the polyglycerols; and
unadecaglycerol in an amount of 0.0 to 7.0 weight% based on the combined
weight of the polyglycerols.
2. A fuel composition according to claim 1 herein the polyglycerol
composition used
to form the polyglycerol ester of a fatty acid comprises a mixture of
diglycerol in an amount of 11.0 to 28.0 weight% based on the combined weight
of
the polyglycerols;
triglycerol in an amount of 9.5 to 24.5 weight% based on the combined weight
of
the polyglycerols;


43

tetraglycerol in an amount of 6.0 to 21.0 weight% based on the combined weight

of the polyglycerols;
pentaglycerol in an amount of 3.5 to 19.0 weight% based on the combined
weight of the polyglycerols;
hexaglycerol in an amount of 6.0 to 13.5 weight% based on the combined weight
of the polyglycerols;
heptaglycerol in an amount of 5.0 to 13.0 weight% based on the combined
weight of the polyglycerols;
octaglycerol in an amount of 4.0 to 12.0 weight% based on the combined weight
of the polyglycerols;
nonaglycerol in an amount of 2.0 to 10.0 weight% based on the combined weight
of the polyglycerols;
decaglycerol in an amount of 0.5 to 8.0 weight% based on the combined weight
of the polyglycerols; and
unadecaglycerol in an amount of 0.1 to 7.0 weight% based on the combined
weight of the polyglycerols.
3. A fuel composition according to claim 1 wherein
the diglycerol comprises acyclic diglycerol in an amount of 6.0 to 25.0
weight%
based on the combined weight of the polyglycerols, and cyclic diglycerol in an
amount of
5.0 to 13.0 weight% based on the combined weight of the polyglycerols
the triglycerol cornprises acyclic triglycerol in an amount of 7.0 to 21.0
weight%
based on the combined weight of the polyglycerols, and cyclic triglycerol in
an arnount of
2.5 to 9.5 weight% based on the combined weight of the polyglycerols;
the tetraglycerol comprises acyclic tetraglycerol in an amount of 5.5 to 15.0
weight% based on the combined weight of the polyglycerols, and cyclic
tetraglycerol in
an amount of 0.5 to 8.0 weight% based on the combined weight of the
polyglycerols; and
the pentaglycerol comprises acyclic pentaglycerol in an amount of 3.0 to 11.0
weight% based on the combined weight of the polyglycerols, and cyclic
pentaglycerol in
an amount of 0.5 to 8.0 weight% based on the combined weight of the
polyglycerols.
4. A fuel composition according to claim 2 wherein
the diglycerol comprises acyclic diglycerol in an amount of 6.0 to 15.0
weight%
based on the combined weight of the polyglycerols, and cyclic diglycerol in an
amount of
5.0 to 13.0 weight% based on the combined weight of the polyglycerols


44

the triglycerol comprises acyclic triglycerol in an amount of 7.0 to 15.0
weight%
based on the combined weight of the polyglycerols, and cyclic triglycerol in
an amount of
2.5 to 9.5 weight% based on the combined weight of the polyglycerols;
the tetraglycerol comprises acyclic tetraglycerol in an amount of 5.0 to 13.0
weight% based on the combined weight of the polyglycerols, and cyclic
tetraglycerol in
an amount of 1.0 to 8.0 weight% based on the combined weight of the
polyglycerols; and
the pentaglycerol comprises acyclic pentaglycerol in an amount of 3.0 to 11.0
weight% based on the combined weight of the polyglycerols, and cyclic
pentaglycerol in
an amount of 0.5 to 8.0 weight% based on the combined weight of the
polyglycerols.
5. A fuel
composition according to any one of the preceding claims wherein the
polyglycerol composition used to form the polyglycerol ester of a fatty acid
comprises a
mixture of
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises diglycerol in an amount of 15.0 to 23.5 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises triglycerol in an amount of 13.5 to 20.5 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises tetraglycerol in an amount of 10.0 to 17.0 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises pentaglycerol in an amount of 8.0 to 14.5 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises hexaglycerol in an amount of 8.0 to 11.5 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises heptaglycerol in an amount of 7.5 to 11.0 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises octaglycerol in an amount of 6.5 to 10.0 weight% based on the
combined
weight of the polyglycerols;

45

the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises nonaglycerol in an amount of 4.0 to 8.0 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises decaglycerol in an amount of 1.5 to 6.0 weight% based on the
combined
weight of the polyolycerols; and
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises unadecaglycerol in an amount of 0.5 to 5.0 weight% based on the
combined
weight of the polyglycerols.
6. A fuel composition according to claim 5 wherein
the diglycerol comprises acyclic diglycerol in an amount of 8.0 to 12.5
weight%
based on the combined weight of the polyglycerols, and cyclic diglycerol in an
amount of
7.5 to 11.0 weight% based on the combined weight of the polyglycerols;
the triglycerol comprises acyclic triglycerol in an amount of 9.0 to 13.0
weight%
based on the combined weight of the polyglycerols, and cyclic triglycerol in
an amount of
4.5 to 7.5 weight% based on the combined weight of the polyglycerols;
the tetraglycerol comprises acyclic tetraglycerol in an amount of 7.5 to 11.0
weight% based on the combined weight of the polyglycerols, and cyclic
tetraglycerol in
an amount of 2.5 to 6.0 weight% based on the combined weight of the
polyglycerols; and
the pentaglycerol comprises acyclic pentaglycerol in an amount of 5.0 to 9.0
weight% based on the combined weight of the polyglycerols, and cyclic
pentaglycerol in
an amount of 2.5 to 6.0 weight% based on the combined weight of the
polyglycerols.
7. A fuel composition according to any one of the preceding claims wherein
the
polyglycerol composition used to form the polyglycerol ester of a fatty acid
comprises a
mixture of
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises diglycerol in an amount of 17.6 to 21.0 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises triglycerol in an amount of 15.9 to 18.1 weight% based on the
combined
weight of the polyglycerols;


46

the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises tetraglycerol in an amount of 12.5 to 14.0 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises pentaglycerol in an amount of 10.5 to 12.2 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises hexaglycerol in an amount of 9.3 to 10.1 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises heptaglycerol in an amount of 8.6 to 9.9 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises octaglycerol in an amount of 7.3 to 8.9 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises nonaglycerol in an amount of 5.5 to 6.4 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises decaglycerol in an amount of 2.9 to 4.5 weight% based on the
combined
weight of the polyglycerols; and
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises unadecaglycerol in an amount of 1.8 to 3.7 weight% based on the
combined
weight of the polyglycerols.
8. A fuel composition according to claim 7 wherein
the diglycerol comprises acyclic diglycerol in an amount of 9.1 to 11.4
weight%
based on the combined weight of the polyglycerols, and cyclic diglycerol in an
amount of
8.5 to 9.5 weight% based on the combined weight of the polyglycerols;
the triglycerol comprises acyclic triglycerol in an amount of 10.0 to 11.8
weight%
based on the combined weight of the polyglycerols, and cyclic triglycerol in
an amount of
5.9 to 6.3 weight% based on the combined weight of the polyglycerols:
the tetraglycerol comprises acyclic tetraglycerol in an amount of 8.4 to 9.5
weight% based on the combined weight of the polyglycerols, and cyclic
tetraglycerol in
an amount of 4.1 to 4.4 weight% based on the combined weight of the
polyglycerols; and

47

the pentaglycerol comprises acyclic pentaglycerol in an amount of 6.7 to 7.6
weight% based on the combined weight of the polyglycerols, and cyclic
pentaglycerol in
an amount of 3.8 to 4.6 weight% based on the combined weight of the
polyglycerols.
9. A fuel composition according to claim 1 wherein in the polyglycerol
composition
used to form the polyglycerol ester of a fatty acid
the digiycerol comprises acyclic diglycerol in an amount of 9.0 to 24.5
weight%
based on the combined weight of the polyglycerols, and cyclic diglycerol in an
amount of
6.5 to 10.0 weight% based on the combined weight of the polyglycerols;
the triglycerol comprises acyclic triglycerol in an amount of 9.0 to 20.5
weight%
based on the combined weight of the polyglycerols, and cyclic triglycerol in
an amount of
3.5 to 6.5 weight% based on the combined weight of the polyglycerols;
the tetraglycerol comprises acyclic tetraglycerol in an amount of 8.0 to 13.5
weight% based on the combined weight of the polyglycerols, and cyclic
tetraglycerol in
an amount of 2.0 to 4.5 weight% based on the combined weight of the
polyglycerols; and
the pentaglycerol comprises acyclic pentaglycerol in an amount of 6.0 to 9.0
weight% based on the combined weight of the polyglycerols, and cyclic
pentaglycerol in
an amount of 2.0 to 5.0 weight% based on the combined weight of the
polyglycerols.
10. A fuel composition according to claim 7 wherein in the polyglycerol
composition
used to form the polyglycerol ester of a fatty acid
the diglycerol comprises acyclic diglycerol in an amount of 20.0 to 26.0
weight%
based on the combined weight of the polyglycerols, and cyclic diglycerol in an
amount of
6.5 to 8.0 weight% based on the combined weight of the polyglycerols;
the triglycerol comprises acyclic trigiycerol in an amount of 18.0 to 21.0
weight%
based on the combined weight of the polyglycerols, and cyclic triglycerol in
an amount of
2.5 to 5.0 weight% based on the combined weight of the polyglycerols;
the tetraglycerol comprises acyclic tetraglycerol in an amount of 11.0 to 14.5

weight% based or the combined weight of the polyglycerols, and cyclic
tetraglycerol in
an amount of 1.5 to 4.0 weight% based on the combined weight of the
polyglycerols; and
the pentaglycerol comprises acyclic pentaglycerol in an amount of 6.5 to 9.5
weight% based on the combined weight of the polyglycerols, and cyclic
pentaglycerol in
an amount of 1.5 to 4.0 weight% based on the combined weight of the
polyglycerols.


48

1. A fuel composition according o any one of the preceding claims wherein
the
polyglycerol composition used to form the polyglycerol ester of a fatty acid
has a hydroxyl
value of from 880 to 1230 mg KOH/g.
12. A fuel composition according to claims 11 wherein the polyglycerol
composition
used to form the polyglycerol ester of a fatty acid has a hydroxyl value of
from 1130 to
1230 mg KOH/g.
13. A fuel composition according to claim 11 wherein the polyglycerol
composition
used to form the polyglycerol ester of a fatty acid has a hydroxyl value of
from 880 to
1060 mg KOH/g.
14. A fuel composition according to claim 11 wherein the polyglycerol
composition
used to form the polyglycerol ester of a fatty acid has a hydroxyl value of
from 950 to
990.
15. A fuel composition according to any one of the preceding claims wherein
the
polyglycerol composition used to form the polyglycerol ester of a fatty acid
has a
refractive index at 25°C of from 1.4855 to 1.4935.
16. A fuel composition according to any one of the preceding claims wherein
the
polyglycerol composition used to form the polyglycerol ester of a fatty acid
has a
refractive index at 50°C of from 1.4895 to 1.4925.
17. A fuel composition according to any one of the preceding claims wherein
the
polyglycerol composition used to form the polyglycerol ester of a fatty acid
has a
refractive index at 50°C of from 1.4900 to 1.4920.
18. A fuel composition according to any one of the preceding claims wherein
the
polyglycerol ester of a fatty acid has a viscosity of less than 700 mPa s at
20°C
19. A fuel composition according to any one of the preceding claims wherein
the
polyglycerol ester of a fatty acid has a viscosity of less than 200 mPa s at
20°C


49

20. A fuel composition according to any one of the preceding claims wherein
the
polyglycerol ester of a fatty acid is prepared by reacting a polyglycerol and
a fatty acid
triglyceride in a ratio of polyglycerol to fatty acid triglyceride of from 1:1
to 1:8.
21. A fuel composition according to any one of the preceding claims wherein
the (b) a
polyglycerol ester of a fatty acid is present in an amount of no greater than
0.5wt% based
on the total fuel composition.
22. A fuel composition according to any one of the preceding claims wherein
the (b) a
polyglycerol ester of a fatty acid is present in an amount of no greater than
0.25wt%
based on the total fuel composition.
23. A fuel composition according to any one of the preceding claims wherein
the (b) a
polyglycerol ester of a fatty acid is present in an amount of no greater than
0.2wt% based
on the total fuel composition.
24. A fuel composition according to any one of the preceding claims wherein
the (b) a
polyglycerol ester of a fatty acid is present in an amount of no greater than
0.1wt% based
on the total fuel composition.
25. A fuel composition according to any one of the preceding claims wherein
the fuel
is selected from diesel, heavy fuel oil, marine gasoil and kerosene.
26 A fuel composition according to claim 25 wherein the fuel is marine
gasoil.
27. A fuel composition according to any one of the preceding claims,
wherein the fuel
composition further comprises (c) water.
28. A fuel composition according to claim 27, wherein the fuel composition
further
comprises (c) water in an amount of from 10 to 70 wt.% based on the total fuel

composition.
29. A fuel composition according to claim 27, wherein the fuel composition
further
comprises (c) water in an amount of from 30 to 60 wt.% based on the total fuel

composition.

50
30. A fuel composition according to claim 27, wherein the fuel composition
further
comprises (c) water in an amount of from 33 to 50 wt.% based on the total fuel

composition.
31 A method for improving the stability of a fuel composition containing
(a) fuel and
(c) water, the method comprising mixing with the fuel and water,
(b) a polyglycerol ester of a fatty acid;
wherein the polyglycerol composition used to form the polyglycerol ester of a
fatty acid
comprises a mixture of
diglycerol in an amount of 11.0 to 34.0 weight% based on the combined weight
of
the polyglycerols;
triglycerol in an amount of 9.5 to 24.5 weight% based on the combined weight
of
the polyglycerols;
tetraglycerol in an amount of 6 0 to 21.0 weight% based on the combined weight

of the polyglycerols;
pentaglycerol in an amount of 3.5 to 19.0 weight% based on the combined
weight of the polyglycerols;
hexaglycerol in an amount of 6 0 to 13.5 weight% based on the combined weight
of the polyglycerols;
heptaglycerol in an amount of 5.0 to 13.0 weight% based on the combined
weight of the polyglycerols,
octaglycerol in an amount of 3.0 to 12.0 weight% based on the combined weight
of the polyglycerols;
nonaglycerol in an amount of 1 5 to 10.0 weight% based on the combined weight
of the polyglycerols;
decaglycerol in an amount of 0.0 to 8 0 weight% based on the combined weight
of the polyglycerols; and
unadecaglycerol in an amount of 0 0 to 7.0 weight% based on the combined
weight of the polyglycerols
32 A method according to claim 31, characterised by the features of any one
of
claims 2 to 30.

51
33. Use of a polyglycerol ester of a fatty acid for improving the stability
of a fuel
composition containing fuel and water;
wherein the polyglycerol composition used to form the polyglycerol ester of a
fatty acid
comprises a mixture of
diglycerol in an amount of 11.0 to 34.0 weight% based on the combined weight
of
the polyglycerols;
triglycerol in an amount of 9.5 to 24.5 weight% based on the combined weight
of
the polyglycerols;
tetraglycerol in an amount of 6.0 to 21.0 weight% based on the combined weight

of the polyglycerols;
pentaglycerol in an amount of 3.5 to 19.0 weight% based on the combined
weight of the polyglycerols;
hexaglycerol in an amount of 6.0 to 13.5 weight% based on the combined weight
of the polyglycerols;
heptaglycerol in an amount of 5.0 to 13.0 weight% based on the combined
weight of the polyglycerols;
octaglycerol in an amount of 3.0 to 12.0 weight% based on the combined weight
of the polyglycerols;
nonaglycerol in an amount of 1.5 to 10.0 weight% based on the combined weight
of the polyglycerols;
decaglycerol in an amount of 0.0 to 8.0 weight% based on the combined weight
of the polyglycerols; and
unadecaglycerol in an amount of 0.0 to 7.0 weight% based on the combined
weight of the polyglycerols.
34. A kit for preparing a fuel composition as defined in any one cf claims
1 to 30, the
kit comprising
a polyglycerol ester of a fatty acid; wherein the polyglycerol composition
used to form the
polyglycerol ester of a fatty acid comprises a mixture of
diglycerol in an amount of 11.0 to 34.0 weight% based on the combined weight
of
the polyglycerols;
triglycerol in an amount of 9.5 to 24.5 weight% based on the combined weight
of
the polyglycerols;
tetraglycerol in an amount of 6.0 to 21.0 weight% based on the combined weight

of the polyglycerols;

52
pentaglycerol in an amount of 3.5 to 19.0 weight% based on the combined
weight of the polyglycerols;
hexaglycerol in an amount of 6.0 to 13.5 weight% based on the combined weight
of the polyglycerols;
heptaglycerol in an amount of 5.0 to 13.0 weight% based on the combined
weight of the polyglycerols;
octaglycerol in an amount of 3.0 to 12.0 weight% based on the combined weight
of the polyglycerols;
nonaglycerol in an amount of 1.5 to 10.0 weight% based on the combined weight
of the polyglycerols;
decaglycerol in an amount of 0.0 to 8.0 weight% based on the combined weight
of the polyglycerols; and
unadecaglycerol in an amount of 0.0 to 7.0 weight% based on the combined
weight of the polyglycerols.
together with instructions for use to prepare the fuel composition.
35. A fuel composition substantially as hereinbefore described with
reference to any
one of the Examples.
36. A method substantially as hereinbefore described with reference to any
one of
the Examples.
37. A use substantially as hereinbefore described with reference to any one
of the
Examples.
38. A kit substantially as hereinbefore described with reference to any one
of the
Examples.

Note: Descriptions are shown in the official language in which they were submitted.

CA 02839237 2013-12-12
WO 2013/001064 PCT/EP2012/062713
1
COMPOSITION
The present invention relates to a composition. In particular the present
invention relates
to fuel compositions having reduced nitrogen oxide emissions when combusted.
As discussed in US 7,491,247 environmental considerations and government
regulations
have increased the need to reduce nitrogen oxide (NOx) production. Nitrogen
oxides
comprise a major irritant in smog and are believed to contribute to
tropospheric ozone
which is a known threat to health. Relatively high flame temperatures reached
in internal
combustion engines, for example diesel-fuelled engines, increase the tendency
for the
production of nitrogen oxides (NOx). These are formed from both the
combination of
nitrogen and oxygen in the combustion chamber and from the oxidation of
organic
nitrogen species in the fuel.
Various methods for reducing NOx production include the use of catalytic
converters,
engine timing changes, exhaust recirculation, and the burning of "clean"
fuels. These
methods are generally too expensive and/or too complicated to be placed in
widespread
use. The rates at which NOx are formed is related to the flame temperature; a
small
reduction in flame temperature can result in a large reduction in the
production of
nitrogen oxides.
has been shown that introducing water into the combustion zone can lower the
flame
temperature and thus lower NOx production, however; the direct injection of
water
requires costly and complicated changes in engine design. Further attempts to
use water
to reduce flame temperature include the use of aqueous fuels, i.e.,
incorporating both
water and fuel into an emulsion. Problems that may occur from long-term use of
aqueous
fuels include precipitate depositions include coalescing ionic species
resulting in filter
plugging and inorganic post combustion deposits resulting in turbo fouling.
Another
problem related to aqueous fuel compositions is that they often require
substantial
engine modifications, such as the addition of in-line homogenizers, thereby
limiting their
commercial utility.
Another method for introducing water into the combustion area is to use fuel
emulsions in
which water is emulsified into a fuel continuous phase, i.e., invert fuel
emulsions. A
problem with these invert fuel emulsions is obtaining and maintaining the
stability of the
emulsion under conventional use conditions. Gravitational phase separation
(during

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storage) and high temperature high pressure/shear flow rate phase separation
(r.,
working engine) of these emulsions present the major hurdle preventing their
commercial
use.
DE-A-3229918 teaches the preparation of emulsions of 25 wt. of water in diesel
oil using
emulsifier which are polyesters of saturated or unsaturated fatty acids having
8-22
carbon atoms. The emulsifiers include polyglycerol esters, sorbitan esters or
diacetyltartaric acid esters of glycerol esters of the fatty acids. The
emulsifiers 2.-'e dosed
in the fuel compositions in amounts of 0.65 to 1.6 wt.%. The diesel emulsions
are taught
to be stable for at least 6 months and, as compared with pure diesel dl used
in engines,
give a better fuel economy, less coke deposition and a lower content of CO and

hydrocarbons in the exhaust gas. In such a system, the emulsifier is
potentially the most
expensive component and dosage at the high levels of this document, such as at
1.6
wt.% would be expensive in use and potentially not commercially viable.
The present invention addresses the problems associated with the use of fuei
emulsion
compositions by providing a stable fuel emulsion composition with the
beneficial
reduction in NOx emissions using commercially viable amounts of emulsifier.
The present invention alleviates the problems of the prior art.
in one aspect the present invention provides a fuel composition comprising:
(a) a fuel; and
(b) a polyglycerol ester of a fatty acid;
wherein the polyglycerol composition used to form the polyglycerol ester of a
fatty acid
comprises a mixture of
diglycerol in an amount of 11.0 to 34.0 weight% based on the combined weight
of the
polyglycerols; triglycerol in an amount of 9.5 to 24.5 weight% based on the
combined
weight of the polyglycerols; tetraglycerol in an amount of 6.0 to 21.0 weight%
based on
the combined weight of the polyglycerols; pentaglycerol in an amount of 3.5 to
19.0
weight% based on the combined weight of the polyglycerols; hexaglycerol in an
amount
of 6.0 to 13.5 weight% based on the combined weight of the polyglycerols;
heptaglycerol
in an amount of 5.0 to 13.0 weight% based on the combined weight of the
polyglycerols;
octagiycerol in an amount of 3.0 to 12.0 weight% based on the combined weight
of the
polyglycerols; nonaglycerol in an amount of 1.5 to 1C.0 weight% based on the
combined

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3
weight of the polyglycerols; decaglycerol in an amount of 0.0 to 8.0 weight%
based on
the combined weight of the polyglycerols; and unadecaglyceroi in an amount of
0.0 to 7.0
weight% based on the combined weight of the polyglycerols.
In one aspect the present invention provides a method for improving the
stability of a fuel
composition containing (a) fuel and (c) water, the method comprising mixing
with the fuel
and water, (b) a polyglycerol ester of a fatty acid;
wherein the polyglycerol composition used to form the polyglycerol ester of a
fatty acid
comprises a mixture of
diglycerol in an amount of 11.0 to 34.0 weight% based on the combined weight
of the
polyglycerols; triglycerol in an amount of 9.5 to 24.5 weight% based on the
combined
weight of the polyglycerols; tetraglycerol in an amount of 6.0 to 21.0 weight%
based on
the combined weight of the polyglycerols; pentaglycerol in an amount of 3.5 to
19.0
weight% based on the combined weight of the polyglycerois; hexaglycerol in an
amount
of 6.0 to 13.5 weight% based on the combined weight of the polyglycerols;
heptaglycerol
in an amount of 5.0 to 13.0 weight% based on the combined weight of the
polyglycerols;
octaglycerol in an amount of 3.0 to 12.0 weight% based on the combined weight
of the
polyglycerols; nonaglycerol in an amount of 1.5 to 10.0 weight% based on the
combined
weight of the polyglycerols; decaglycerol in an amount of 0.0 to 8.0 weight%
based on
the combined weight of the polyglycerols; and unadecaglycerol in an amount of
0.0 to 7.0
weight% based on the combined weight of the polyglycerols.
In one aspect the present invention provides a kit for preparing a fuel
composition as
defined herein, the kit comprising a poiyglycerol ester of a fatty acid as
described herein;
together with instructions for use to prepare a fuel composition containing
fuel and water.
in one aspect the present invention provides use of a polyglycerol ester of a
fatty acid for
improving the stability of a fuel composition containing fuel and water;
wherein the polyglycerol composition used to form the polyglycero ester of a
fatty acid
comprises a mixture of
diglycerol in an amount of 11.0 to 34.0 weight% based on the combined weight
of the
polyglycerols; triglycerol in an amount of 9.5 to 24.5 weight% based on the
combined
weight of the polyglycerols; tetraglycerol in an amount of 6.0 to 21.0 weight%
based on
the combined weight of the polyglycerols; pentaglycerol in an amount of 3.5 to
19.0
weight% based on the combined weight of the polyglycerols; hexaglycerol in an
amount

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4
of 6.0 to 13.5 weight% based on the combined weight of the polyglycercis;
her,taglycerol
in an amount of 5.0 to 13.0 weiaht% based on the combined weight of the
po!yalycerols;
octaglyceml in an amount of 3.0 to 12.0 weight% based on the combined weight
of the
polyglycerols; nonaglyceroi in an amount of 1.5 to 10.0 weight% based on the
combined
weight of the polyglycerols; decaglycerol in an amount of 0.0 to 8.0 weight%
based on
the combined weight of the polyglycerols; and unadecaglycerol in an amount of
0.0 to 7.0
weight% based on the combined weight of the polyglycerols.
We have shown that when a polyglycerol composition is used which has
predominantly
one polyglycerol present, such as diglycerol or triglycerol, then the
polyglycerol
composition must be present in a significantly higher amount to provide a
fuel/water
emulsion which is stable during storage. In contrast we have surprisingly
found that
having a broad range of polyglycerols present in a polyglycerol composition,
and in
particular the specific ranges recited herein, then a lower and therefore
commercially
viable amount of emulsifiers may be used while still providing a fuel and
water emulsion
which is stable over the period required in use, such as 3 hours. The "flat"
distribution of
polyglycerols allows for this enhanced effect at low dosages. By flat
distribution it is
meant that the polyglycerols contain a broad range of polyglycerols chain
lengths and the
broad range of polyglycerols are present in an amount such that only a few
polyglycerol
chain lengths dominate the distribution of polyglycerols. For example in a
flat distribution
one or two polyglycerol chain lengths do not make up 70 or 80% of the total
amount of
polyglycerols.
For ease of reference these and further aspects of the present invention are
now
discussed under appropriate section headings. However, the teachings under
each
section are not necessarily limited to each particular section.
Composition
As previously mentioned, in one aspect the present invention provides a fuel
composition
comprising:
(a) a fuel; and
(b) a polyglycerol ester of a fatty acid;
wherein the polyglycerol composition used to form the polyglycerol ester of a
fatty acid
comprises a mixture of

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diglycerol in an amount of 11.0 to 34.0 weight% based on the combined weight
of the
polyglycerols; triglycerol in an amount of 9.5 to 24.5 weight% based on the
combined
weight of the polyglycerols; tetragiycerol in an amount of 6.0 to 21.0 weight%
based on
the combined we,ight of the polyglycerols; pentaglycerol in an amount of 3.5
to 19.0
5 weight%
based on the combined weight of the polyglycerols; hexaglycerol in an amount
of 6.0 to 13.5 weight% based on the combined weight of the polyglycerols;
heptagiyceroi
in an amount of 5.0 to 13.0 weight% based on the combined weight of the
polyglycerols;
octaglycerol in an amount of 3.0 to 12.0 weight% based on the combined weight
of the
polyglycerols; nonaglycerol in an amount of 1.5 to 10.0 weight% based on the
combined
weight of the polyglycerols; decaglycerol in an amount of 0.0 to 8.0 weight%
based on
the combined weight of the polyglycerols; and unadecaglycerol in an amount of
0.0 to 7.0
weight% based on the combined weight of the polyglycerols.
Polyglycerol Ester of a Fatty Acid
As is understood by one skilled in the art polyglycerol ester of a fatty acid
is an emulsifier
comprising a polyglycerol 'backbone' onto which fatty acid side chains are
attached.
Polyglycerol esters of fatty acids are typically prepared by polymerisation of
glycerol to
provide one or more polyglycerols to which the fatty acids are then attached.
The fatty
acids are generally attached by one of two routes. A first route involves the
direct
attachment of the fatty acid to the polyglycerol. The second route involves
inter-
esterifying a polyglycerol and a triglyceride thereby transferring fatty acids
from the
triglyceride to the polyglyceroi. The polymerisation of glycerol typically
provides a mixture
of polyglycerols of different degrees of polymerisation. The mixture of
polyglycerols of
different degrees of polymerisation is described herein as a polyglycerol
composition. it
will be understood by one skilled in the art that references to a polyglycerol
composition
having particular polyglycerol components requires only that those components
be
present in the amount specified. it will be appreciated by one skilled in the
art that
because of the nature of polymerisation of glycerol, the polyglycerol
composition may
contain other polyglycerols having degrees of polymerisation not recited
herein. in
determining the amounts of polyglycerols in the polyglycerol composition, the
total
amount of all polyglycerols (irrespective of degree of polymerisation) is
determined to
provide the total weight of the polyglycerol composition. Materials which are
not a

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6
polyglycerol do not form part of the polyglycerol composition and their weight
is not
considered when determining the total weight of the polygiycerol composition.
References in the present specification to "the combined weight of the
polyglycerols"
encompass the total combined weight of all polyglycerols, irrespective of
their chain
length and irrespective of whether the poiyglycerol is recited in the listing
of
polyglycerols.
As discussed here in the polyglycerol composition used to form the
polyglycerol ester of
to a fatty acid comprises a mixture of diglycerol in an amount of 11.0 to
34.0 weight%
based on the combined weight of the polyglycerols; triglycerol in an amount of
9.5 to 24.5
weight% based on the combined weight of the polyglycerols; tetraglyceroi in an
amount
of 6.0 to 21.0 weight% based on the combined weight of the polyglycerols;
pentaglycerol
in an amount of 3.5 to 19.0 weight% based on the combined weight of the
polyglycerols;
hexagiycerol in an amount of 6.0 to 13.5 weight% based on the combined weight
of the
polyglycerols; heptaglycerol in an amount of 5.0 to 13.0 weight% based on the
combined
weight of the polyglycerols: octaglycerol in an amount of 3.0 to 12.0 weight%
based on
the combined weight of the polyglycerols; nonaglycerol in an amount of 1.5 to
10.0
weight% based on the combined weight of the polyglycerols; decaglycerol in an
amount
of 0.0 to 8.0 weight% based on the combined weight of the polyglycerols; and
unadecaglycerol in an amount of 0.0 to 7.0 weight% based on the combined
weight of
the polyglycerols.
It will be appreciated by one skilled in the art that polyglycerols may be
either in the form
of a cyciic polyglycerol or an acyclic polygiycerol. Acyclic polyglycerols are
straight chain
and branched chain polyglycerols, that is acyclic polyglycerols are formed
entirely from
glycerol groups linked such that no rings are formed. Cyclic polyglycerols
contain a ring
structure. References in the present specification to a polyglycerol of a
particular degree
of polymerisation, for example triglycerol referring to a polyglycerol having
a degree of
polymerisation of 3, include both the polyglycerol in cyclic form and in
acyclic form. VVe
have further determined the preferred amounts of cyclic and acyclic
polyglycerols for
each of diglycerol, triglycerol, tetraglycerol and pentaglycerol. In one
preferred aspect the
diglycerol comprises acyclic diglycerol in an amount of 6.0 to 25.0 weight%
based on the
combined weight of the polyglycerols, and cyclic diglycerol in an amount of
5.0 to 13.0
weight% based on the combined weight of the polyglycerols. In one preferred
aspect the

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7
triglycerol comprises acyclic triglycerol in an amount of 7.0 to 21.0 weight%
based on the
combined weight of the polyglycerols, and cyclic triglycerol in an amount of
2.5 to 9.5
weight% based on the combined weight of the polyglycerols. in one preferred
aspect the
tetraglycerol comprises acyclic tetragiycerol in an amount of 5.5 to 15.0
weight% based
on the combined weight of the polyglycerols, and cyclic tetraglycerol in an
amount of 0.5
to 8.0 weight% based on the combined weight of the polyglycerois. in one
preferred
aspect the pentaglycerol comprises acyclic pentaglycerol in an amount of 3.0
to 11.0
weight% based on the combined weight of the polyglycerols, and cyclic
pentaglycerol in
an amount of 0.5 to 8.0 weight% based on the combined weight of the
polyglycerols.
In one preferred aspect
the diglycero! comprises acyclic diglycerol in an amount of 6.0 to 25.0
weight%
based on the combined weight of the polyglycerols, and cyclic diglycerol in an
amount of
5.0 to 13.0 weight% based on the combined weight of the polyglycerols;
the triglycerol comprises acyclic triglycerol in an amount of 7.0 to 21.0
weight%
based on the combined weight of the polyglycerols, and cyclic triglycerol in
an amount of
2.5 to 9.5 weight% based on the combined weight of the polyglycerols;
the tetraglycerol comprises acyclic tetraglycerol in an amount of 5.5 to 15.0
weight% based on the combined weight of the polyglycerols, and cyclic
tetraglycerol in
an amount of 0.5 to 8.0 weight% based on the combined weight of the
polyglycerols; and
the pentaglycerol comprises acyclic pentaglycerol in an amount of 3.0 to 11.0
weight% based on the combined weight of the polyglycerols, and cyclic
pentaglycerol in
an amount of 0.5 to 8.0 weight% based on the combined weight of the
polyglycerols.
In one preferred aspect the diglycerol comprises acyclic diglycerol in an
amount of 6.0 to
15.0 weight% based on the combined weight of the polyglycerols, and cyclic
diglycerol in
an amount of 5.0 to 13.0 weight% based on the combined weight of the
polyglycerols. In
one preferred aspect the triglycerol comprises acyclic triglycerol in an
amount of 7.0 to
15.0 weight% based on the combined weight of the polyglycerols, and cyclic
triglycerol in
an amount of 2.5 to 9.5 weight% based on the combined weight of the
polyglycerols. In
one preferred aspect the tetraglycerol comprises acyclic tetraglycerol in an
amount of 5.0
to 13.0 weight% based on the combined weight of the polyglycerols, and cyclic
tetraglycerol in an amount of 0.5 to 8.0 weight% based on the combined weight
of the
polyglycerols. In one preferred aspect the pentaglycerol comprises acyclic
pentaglycerol
in an amount of 3.0 to 11.0 weight% based on the combined weight of the
polyglycerols,

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8
and cyclic pentaglycerol in an amount of 0.5 to 8.0 weight% based on the
combined
weight of the polyglycerols.
in one preferred aspect the diglycerol comprises acyclic diglyceroi in an
amount of 6.0 to
15.0 weight% based on the combined weight of the polygiycerols, and cyclic
diglycerol in
an amount of 5.5 to 13.0 weight% based on the combined weight of the
polyglycerols. In
one preferred aspect the triglycerol comprises acyclic triglycerol in an
amount of 7.0 to
15.0 weight% based on the combined weight of the polyglycerols, and cyclic
triglycerol in
an amount of 2.5 to 9.5 weight% based on the combined weight of the
polyglycerols. In
one preferred aspect the tetraglycerol comprises acyclic tetraglycerol in an
amount of 5.0
to 13.0 weight% based on the combined weight of the polyglycerols, and cyclic
tetraglycerol in an amount of 0.5 to 8.0 weight% based on the combined weight
of the
polyglycerols. In one preferred aspect the pentaglycerol comprises acyclic
pentaglycerol
in an amount of 3.0 to 11.0 weight% based on the combined weight of the
polyglycerols,
and cyclic pentaglycerol in an amount of 0.5 to 8.0 weight% based on the
combined
weight of the polyglycerols.
In one preferred aspect
the diglycerol comprises acyclic diglycerol in an amount of 6.0 to 15.0
weight%
based on the combined weight of the polyglycerois, and cyclic diglycerol in an
amount of
5.5 to 13.0 weight% based on the combined weight of the polyglycerols
the triglycerol comprises acyclic triglycerol in an amount of 7.0 to 15.0
weight%
based on the combined weight of the polyglycerols, and cyclic triglycerol in
an amount of
2.5 to 9.5 weight% based on the combined weight of the polyglycerols;
the tetraglycerol comprises acyclic tetraglycerol in an amount of 5.0 to 13.0
weight% based on the combined weight of the polyglycerols, and cyclic
tetraglycerol in
an amount of 0.5 to 8.0 weight% based on the combined weight of the
polyglycerols; and
the pentaglycerol comprises acyclic pentaglycerol in an amount of 3.0 to 11.0
weight% based on the combined weight of the polyglycerols, and cyclic
pentaglycerol in
an amount of 0.5 to 8.0 weight% based on the combined weight of the
polyglycerols.
In one preferred aspect
the diglycerol comprises acyclic diglycerol in an amount of 6.0 to 15.0
weight%
based on the combined weight of the polyglycerols, and cyclic diglycerol in an
amount of
5.5 to 13.0 weight% based on the combined weight of the polyglycerols

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the triglycerol comprises acyclic triglycerol in an amount of 7.0 to 15.0
weight%
based on the combined weight of the polyglycerols, and cyclic triglycerol in
an amount of
2.5 to 9.5 weight% based on the combined weight of the polyglycerols;
the tetraglycerol comprises acyclic tetraglyceral in en amount of 5.0 to 13.0
weight% based on the combined weight of the polyglycerols, and cyclic
tetraglycerol in
an amount of 1.0 to 8.0 weight% based on The combined weight of the
polyglycerols; and
the pentaglycerol comprises acyclic pentaglycerol in an amount of 3.0 to 11.0
weight% based on the combined weight of the polyglycerols, and cyclic
pentaglycerol in
an amount of 0.5 to 8.0 weight% based on the combined weight of the
polyglycerois.
!()
In one preferred aspect the polyglycerol composition used to form the
polyglycerol ester
of a fatty acid comprises a mixture of
acyclic diglycerol in an amount of 6.0 to 15.0 weight% based on the combined
weight of the polyglycerols, and cyclic diglycerol in an amount of 5.5 to 13.0
weight%
based on the combined weight of the polyglycerols
acyclic triglycerol in an amount of 7.0 to 15.0 weight% based on the combined
weight of the polyglycerols, and cyclic triglycerol in an amount of 2.5 to 9.5
weight%
based on the combined weight of the polyglycerols;
acyclic tetraglycerol in an amount of 5.0 to 13.0 weight% based on the
combined
weight of the polyglycerols, and cyclic tetraglycerol in an amount of 0.5 to
8.0 weight%
based on the combined weight of the poiyglycerols; and
acyclic pentaglycerol in an amount of 3.0 to 11.0 weight% based on the
combined
weight of the polyglycerols, and cyclic pentaglycerol in an amount of 0.5 to
8.0 weight%
based on the combined weight of the polyglycerols.
25. hexaglycerol in an amount of 6.0 to 13.5 weight% based on the combined
weight
of the polyglycerols
heptaglycerol in an amount of 5.0 to 13.0 weight% based on the combined
weight of the polyglycerols
octaglycerol in an amount of 4.0 to 12.0 weight% based on the combined weight
of the polyglycerols
nonaglycerol in an amount of 2.0 to 10.0 weight% based on the combined weight
of the polyglycerols
decaglycerol in an amount of 0.5 to 8.0 weight% based on the combined weight
of the polyglycerols; and

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=
unadecaglycerol n an amount of 0.1 to 7.0 weight% based on the combined
weight of the polyglycerols.
In one preferred aspect the polyglycerol composition used to form the
polyglycerol ester
5 of a fatty acid comprises a mixture of
acyclic diglycerol in an amount of 6.0 to 15.0 weight% based on the combined
weight of the polyglycerols, and cyclic diglycerol in an amount of 5.0 to 13.0
weight%
based on the combined weight of the polyglycerols
acyclic triglycerol in an amount of 7.0 to 15.0 weight% based on the combined
to weight
of the polyglycerols, and cyclic triglycerol in an amount of 2.5 to 9.5
weight%
based on the combined weight of the polyglycerols;
acyclic tetraglycerol in an amount of 5.0 to 13.0 weight% based on the
combined
weight of the polyglycerols, and cyclic tetraglycerol in an amount of 1.0 to
8.0 weight%
based on the combined weight of the polyglycerols; and
acyclic pentaglycerol in an amount of 3.0 to 11.0 weight% based on the
combined
weight of the polyglycerols, and cyclic pentaglycerol in an amount of 0.5 to
8.0 weight%
based on the combined weight of the polyglycerols.
hexaglycerol in an amount of 6.0 to 13.5 weight% based on the combined weight
of the polyglycerols
heptaglycerol in an amount of 5.0 to 13.0 weight% based on the combined
weight of the polyglycerols
octaglycerol in an amount of 4.0 to 12.0 weight% based on the combined weight
of the polyglycerols
nonaglycerol in an amount of 2.0 to 10.0 weight% based on the combined weight
of the polyglycerols
decaglycerol in an amount of 0.5 to 8.0 weight% based on the combined weight
of the polyglycerols; and
unadecaglycerol in an amount of 0.1 to 7.0 weight% based on the combined
weight of the polyglycerols.
ln one preferred aspect the polyglycerol composition used to form the
polyglycerol ester
of a fatty acid comprises diglycerol in an amount of 15.0 to 23.5 weight%
based on the
combined weight of the polyglycerols. In one preferred aspect the polyglycerol

composition used to form the polyglycerol ester of a fatty acid comprises
triglycerol in an
amount of 13.5 to 20.5 weight% based on the combined weight of the
polyglycerols. In

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one preferred aspect the polyglycerol composition used to form the
polyglycerol ester of
a fatty acid comprises tetraglycerol in an amount of 10.0 to 17.0 weight%
based on the
combined weight of the polyglycerols. In one preferred aspect the polyglycerol

composition used to form the polyglycerol ester of a fatty acid comprises
pentaglycerol in
an amount of 3.0 to 14.5 weight% based on the combined weight of the
polyglycerols. In
one preferred aspect the polygiycerol composition used to form the poygiycerol
ester of
a fatty acid comprises hexaglycerol in an amount of 8.0 to 11.5 weight% based
on the
combined weight of the polyglycerols. In one preferred aspect the polygiycerol

composition used to form the polyglycerol ester of a fatty acid comprises
heptaglycerol in
an amount of 7.5 to 11.0 weight% based on the combined weight of the
polyglycerols. In
one preferred aspect the polyglycerol composition used to form the
polyglycerol ester of
a fatty acid comprises octaglycerol in an amount of 6.5 to 10.0 weight% based
on the
combined weight of the polyglycerols. in one preferred aspect the polygiyceroi

composition used to form the polyglycerol ester of a fatty acid comprises
nonaglycerol in
Is an amount of 4.0 to 8.0 weight% based on the combined weight of the
polyglycerols. In
one preferred aspect the polyglycerol composition used to form the
polyglycerol ester of
a fatty acid comprises decaglycerol in an amount of 1.5 to 6.0 weight% based
on the
combined weight of the polyglycerols. In one preferred aspect the polyglycerol

composition used to form the polyglycerol ester of a fatty acid comprises
unadecaglycerol in an amount of 0.5 to 5.0 weight% based on the combined
weight of
the polyglycerols.
In one preferred aspect the polyglycerol composition used to form the
polyglycerol ester
of a fatty acid comprises a mixture of
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises diglycerol in an amount of 15.0 to 23.5 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises triglycerol in an amount of 13.5 to 20.5 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the poiyglycerol ester of a fatty
acid
comprises tetraglycerol in an amount of 10.0 to 17.0 weight% based on the
combined
weight of the polyglycerols;

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the polyglycerol composition used to form the polyglyceroi ester of a fatty
acid
comprises pentaglycerol in an amount of 8.0 to 14.5 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycero! ester of a fatty
acid
comprises hexaglycerol in an amount of 8.0 to 11.5 weight% based on the
combined
weight of the polyglycerols;
the poiyglycerol composition used to form the polyglyceral ester of a fatty
acid
comprises heptaglycerol in an amount of 7.5 to 11.0 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises octaglycerol in an amount of 6.5 to 10.0 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises nonaglycerol in an amount of 4.0 to 8.0 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises decaglycerol in an amount of 1.5 to 6.0 weight% based on the
combined
weight of the polyglycerols; and
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises unadecaglycerol in an amount of 0.5 to 5.0 weight% based on the
combined
weight of the polyglycerols.
In one preferred aspect the diglycerol comprises acyclic diglycerol in an
amount of 8.0 to
12.5 weight% based on the combined weight of the polyglycerols, and cyclic
diglycerol in
an amount of 7.5 to 11.0 weight% based on the combined weight of the
polyglycerols. In
one preferred aspect the triglycerol comprises acyclic triglycerol in an
amount of 9.0 to
13.0 weight% based or the combined weight of the polyglycerols, and cyclic
triglycerol in
an amount of 4.5 to 7.5 weight% based on the combined weight of the
polyglycerols. in
one preferred aspect the tetraglycerol comprises acyclic tetraglycerol in an
amount of 7.5
to 11.0 weight% based on the combined weight of the polyglycerols, and cyclic
tetraglycerol in an amount of 2.5 to 6.0 weight% based on the combined weight
of the
polyglycerols. In one preferred aspect the pentaglycerol comprises acyclic
pentaglycerol
in an amount of 5.0 to 9.0 weight% based on the combined weight of the
polyglycerols,
and cyclic pentaglycerol in an amount of 2.5 to 6.0 weight% based on the
combined
weight of the polyglycerols.

CA 02839237 2013-12-12
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13
!ri one preferred aspect
the diglycerol comprises acyclic diglycerol in an amount of 8.0 to 12.5
weight%
based on the combined weight of the potyglycerols, and cyclic diglycerol 41 an
amount of
7.5 to 11.0 weight% based on the combined weight of the polyglycerols;
the triglycerol compnses acyclic triglycerol in an amount of 9.0 to 13.0
weight%
based on the combined weight of the polyglycerols, and cyclic triglycerol in
an amount of
4.5 to 7.5 weight% based on the combined weight of the polyglycerols;
the tetraglycerol comprises acyclic tetraglycerol in an amount of 7.5 to 11.0
i 0 weight% based on the combined weight of the polyglycerols, and cyclic
tetraglyceroi in
an amount of 2.5 to 6.0 weight% based on the combined weight of the
polyglycerols; and
the pentaglycerol comprises acyclic pentaglycerol in an amount of 5.0 to 9.0
weight% based on the combined weight of the polyglycerols, and cyclic
pentaglyceroi in
an amount of 2.5 to 6.0 weight% based on the combined weight of the
polyglycerols.
In one preferred aspect the polyglycerol composition used to form the
polyglycerol ester
of a fatty acid comprises a mixture of
acyclic diglycerol in an amount of 8.0 to 12.5 weight% based on the combined
weight of the polyglycerols, and cyclic diglycerol in an amount of 7.5 to 11.0
weight%
based on the combined weight of the polyglycerols;
acyclic triglycerol in an amount of 9.0 to 13.0 weight% based on the combined
weight of the polyglycerols, and cyclic triglycerol in an amount of 4.5 to 7.5
weight%
based on the combined weight of the polyglycerols;
acyclic tetraglycerol in an amount of 7.5 to 11.0 weight% based on the
combined
weight of the polyglycerols, and cyclic tetraglycerol in an amount of 2.5 to
6.0 weight%
based on the combined weight of the polyglycerols; and
acyclic pentaglycerol in an amount of 5.0 to 9.0 weight% based on the combined

weight of the polyglycerols, and cyclic pentaglycerol in an amount of 2.5 to
6.0 weight%
based on the combined weight of the polyglycerols.
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises hexaglycerol in an amount of 8.0 to 11.5 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises heptaglycerol in an amount of 7.5 to 11.0 weight% based on the
combined
weight of the polyglycerols;

CA 02839237 2013-12-12
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14
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises octaglycerol in an amount of 6.5 to 10.0 weight% based on the
combined
weight of the polyglycerols;
the polygiycerol composition used to form the polyglycero! ester of a fatty
acid
comprises nonaglycerol in an amount of 4.0 to 8.0 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises decaglyceroi in an amount of 1.5 to 6.0 weight% based on the
combined
weight of the polyglycerois; and
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises unadecaglycerol in an amount of 0.5 to 5.0 weight% based on the
combined
weight of the polyglycerois.
in one preferred aspect the polygiycerol composition used to form the
polyglycerol ester
of a fatty acid comprises diglycerol in an amount of 17.6 to 21.0 weight%
based on the
combined weight of the poiyglycerols. In one preferred aspect the polyglycero:

composition used to form the polyglycerol ester of a fatty acid comprises
triglycerol in an
amount of 15.9 to 18.1 weight% based on the combined weight of the
polyglycerols. In
one preferred aspect the polyglycerol composition used to form the
polyglycerol ester of
a fatty acid comprises tetraglycerol in an amount of 12.5 to 14.0 weight%
based on the
combined weight of the polyglycerols. In one preferred aspect the polyglycerol

composition used to form the polyglycerol ester of a fatty acid comprises
pentaglycerol in
an amount of 10.5 to 12.2 weight% based on the combined weight of the
polyglycerols.
In one preferred aspect the polyglycerol composition used to form the
polyglycerol ester
of a fatty acid comprises hexaglycerol in an amount of 9.3 to 10.1 weight%
based on the
combined weight of the polyglycerols. In one preferred aspect the polyglycerol

composition used to form the polyglycerol ester of a fatty acid comprises
heptaglycerol in
an amount of 8.6 to 9.9 weight% based on the combined weight of the
polyglycerols. In
one preferred aspect the polyglycerol composition used to form the
polyglycerol ester of
a fatty acid comprises octaglycerol in an amount of 7.3 to 8.9 weight% based
on the
combined weight of the polyglycerols. In one preferred aspect the polyglycerol

composition used to form the polyglycerol ester of a fatty acid comprises
nonaglycerol in
an amount of 5.5 to 6.4 weight% based on the combined weight of the
polyglycerols. In
one preferred aspect the polyglycerol composition used to form the
polyglycerol ester of
a fatty acid comprises decaglycerol in an amount of 2.9 to 4.5 weight% based
on the

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16
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises unadecaglycero in an amount of 1.8 to 3.7 weight% based on the
combined
weight of the polyglycerols.
In one preferred aspect the diglycerol comprises acyclic diglycerol in an
amount of 9:1 to
11.4 weight% based on the combined weight of the polyglycerols, and cyclic
diglycerol in
an amount of 8.5 to 9.5 weight% based on the combined weight of the
polyglycerols. In
one preferred aspect the triglycerol comprises acyclic triglycerol in an
amount of 10.0 to
11.8 weight% based on the combined weight of the polyglycerols, and cyclic
triglycerol in
an amount of 5.9 to 6.3 weight% based on the combined weight of the
polyglycerols. In
one preferred aspect the tetraglycerol comprises acyclic tetraglycerol in an
amount of 8.4
to 9.5 weight% based on the combined weight of the polyglycerols, and cyclic
tetraglycerol in an amount of 4.1 to 4.4 weight% based on the combined weight
of the
polyglycerols. in one preferred aspect the pentaglycerol comprises acyclic
pentaglycerol
in an amount of 6.7 to 7.6 weight% based on the combined weight of the
polyglycerols,
and cyclic pentagiycerol in an amount of 3.8 to 4.6 weight% based on the
combined
weight of the polyglycerols.
In one preferred aspect
the diglycerol comprises acyclic diglycerol in an amount of 9.1 to 11.4
weight%
based on the combined weight of the polyglycerols, and cyclic diglycerol in an
amount of
8.5 to 9.5 weight% based on the combined weight of the polyglycerols;
the triglycerol comprises acyclic triglycerol in an amount of 10.0 to 11.8
weight%
based on the combined weight of the polygiycerols, and cyclic trigiycero! in
an amount of
5.9 to 6.3 weight% based on the combined weight of the polyglycerols;
the tetraglycerol comprises acyclic tetraglyceroi in an amount of 8.4 to 9.5
weight% based on the combined weight of the polyglycerols, and cyclic
tetraglycerol in
an amount of 4.1 to 4.4 weight% based on the combined weight of the
polyglycerols; and
the pentagiycerol comprises acyclic pentagiycerol in an amount of 6.7 to 7.6
weight% based on the combined weight of the polyglycerols, and cyclic
pentaglycerol in
an amount of 3.8 to 4.6 weight% based on the combined weight of the
polyglycerols.
!n one preferred aspect the polyglycerol composition used to form the
polyglycerol ester
of a fatty acid comprises a mixture of

CA 02839237 2013-12-12
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17
acyclic diglycerol in an amount of 9.1 to 1=! .4 weight% based on the combined

weight of the polyglycerols, and cyclic digiycerol in an amount of 8.5 to 9.5
weioht%
based on the combined weight of the polyglycerols;
acyclic triglycerol in an amount of 10.0 to 11.8 weight% based on the combined
weight of the polyglycerols, and cyclic triglycerol in an amount of 5.9 to 6.3
weight%
based on the combined weight of the polyglycerols;
acyclic tetraglycerol in an amount of 8.4 to 9.5 weight% based on the combined

weight of the polyglycerois, and cyclic tetraglycerol in an amount of 4.1 to
4.4 weight%
based on the combined weight of the polyglycerols; and
acyclic pentaglyceroi in an amount of 6.7 to 7.6 weight% based on the combined
weight of the polyglycerols, and cyclic pentaglycerol in an amount of 3.8 to
4.6 weight%
based on the combined weight of the polyglycerols.
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises hexaglycerol in an amount of 9.3 to 10.1 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises heptaglyceroi in an amount of 8.6 to 9.9 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycero! ester of a fatty
acid
comprises octaglyceroi in an amount of 7.3 to 8.9 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises nonaglycerol in an amount of 5.5 to 6.4 weight% based on the
combined
weight of the polyglycerols;
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises decaglycerol in an amount of 2.9 to 4.5 weight% based on the
combined
weight of the polyglycerols; and
the polyglycerol composition used to form the polyglycerol ester of a fatty
acid
comprises unadecaglycerol in an amount of 1.8 to 3.7 weight% based on the
combined
weight of the polyglycerois.
in one preferred aspect the polyglycerol composition used to form the
polyglycerol ester
of a fatty acid comprises diglycerol in an amount of 18.0 to 32.0 weight%
based on the
combined weight of the polyglycerois. In one preferred aspect the polyglycerol
composition used to form the polyglycerol ester of a fatty acid comprises
triglycerol in an

CA 02839237 2013-12-12
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18
amount of 16.0 to 24.0 weight% based on the combined weight of the
poiyglycerols. In
one preferred aspect the polygiyceroi composition used to form the
polyglyceroi ester of
a fatty acid comprises tetraglycerol in an amount of 12.0 to 16.0 weight%
based on the
combined weight of the polyglycerols. In one preferred aspect the polyglycerol
composition used to form the polyglyceroi ester of a fatty acid comprises
pentagiycerol in
an amount of 8.0 to 12.0 weight% based on the combined weight of the
polyglycerols. in
one preferred aspect the poiyglycerol composition used to form the
polyglycerol ester of
a fatty acid comprises hexaglyceroi in an amount of 7.0 to 11.0 weight% based
on the
combined weight of the poiyglycerols. in one preferred aspect the polyglycerol
lo composition used to form the polyglycerol ester of a fatty acid
comprises heptaglycerol in
an amount of 5.0 to 10.0 weight% based on the combined weight of the
polyglycerols. In
one preferred aspect the polyglycerol composition used to form the
polyglycerol ester of
a fatty acid comprises octaglycerol in an amount of 3.0 to 9.0 weight% based
on the
combined weight of the polyglycerols. In one preferred aspect the polyglyceroi
composition used to form the polyglyceroi ester of a fatty acid comprises
nonaglycerol in
an amount of 1.5 to 7.0 weight% based on the combined weight of the
polyglycerols. In
one preferred aspect the poiyglycerol composition used to form the
polygiycerol ester of
a fatty acid comprises decaglycerol in an amount of 0.0 to 4.5 weight% based
on the
combined weight of the polyglycerols. In one preferred aspect the polyglycerol
composition used to form the polyglycerol ester of a fatty acid comprises
unadecaglycerol in an amount of 0.0 to 4.0 weight% based on the combined
weight of
the polyglycerols.
In one preferred aspect the polyglycerol composition used to form the
polyglycerol ester
of a fatty acid comprises a mixture of
diglycerol in an amount of 18.0 to 32.0 weight% based on the combined weight
of the polyglycerols;
triglycerol in an amount of 16.0 to 24.0 weight% based on the combined weight
of the polyglycerols;
tetraalycerol in an amount of 12.0 to 16.0 weight% based on the combined
weight of the polyglycerols;
pentaglycerol in an amount of 8.0 to 12.0 weight% based on the combined
weight of the poiyglycerols;
hexaglycerol in an amount of 7.0 to 11.0 weight% based on the combined weight
of the polyglycerols;

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19
heptaglycerol in an amount of 5.0 to 10.0 weight% based on the combined
weight of the polyglycerols;
octaglyceroi in an amount of 3.0 to 9.0 weight% based on the combined weight
of the poiyglycerois;
nonaglycerol in an amount of 1.5 to 7.0 weight% based on the combined weight
of the polyglycerols;
decaglycerol in an amount of 0.0 to 4.5 weight% based on the combined weight
of the polyglycerols; and
unadecaalycerol in an amount of 0.0 to 4.0 weight% based on the combined
weight of the polyglycerois.
In one preferred aspect the diglycerol comprises acyclic diglycerol in an
amount of 9.0 to
24.5 weight% based on the combined weight of the polyglycerols, and cyclic
diglycerol in
an amount of 6.5 to 10.0 weight% based on the combined weight of the
polyglycerols. In
one preferred aspect the triglycerol comprises acyclic triglycerol in an
amount of 9.0 to
20.5 weight% based on the combined weight of the polyglycerols, and cyclic
triglycerol in
an amount of 3.5 to 6.5 weight% based on the combined weight of the
polyglycerols. In
one preferred aspect the tetraglycerol comprises acyclic tetraglycerol in an
amount of 8.0
to 13.5 weight% based on the combined weight of the polyglycerols, and cyclic
tetraglycerol in an amount of 2.0 to 4.5 weight% based on the combined weight
of the
polyglycerols. In one preferred aspect the pentaglycerol comprises acyclic
pentaglycerol
in an amount of 6.0 to 9.0 weight% based on the combined weight of the
polyglycerols,
and cyclic pentaglycerol in an amount of 2.0 to 5.0 weight% based on the
combined
weight of the polyglycerols.
In one preferred aspect in the polyglycerol composition used to form the
polyglyceroi
ester of a fatty acid
the diglycerol comprises acyclic diglycerol in an amount of 9.0 o 24.5 weight%

based on the combined weight of the polyglycerols, and cyclic diglycerol in an
amount of
6.5 to 10.0 weight% based on the combined weight of the polyglycerols;
the triglycerol comprises acyclic triglycerol in an amount of 9.0 to 20.5
weight%
based on the combined weight of the polyglycerols, and cyclic triglycerol in
an amount of
3.5 to 6.5 weight% based on the combined weight of the polyglycerols;

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the tetragiycerol comprises acyclic tetraglycerol in an amount of 8.0 to 13.5
weight% based on the combined weight of the poiyglycerols, and cyclic
tetraglycerol in
an amount of 2.0 to 4.5 weight% based on the combined weight of the
polyglycerols; and
the pentaglycerol comprises acyclic pentaglycerol in an amount of 6.0 to 9.0
5 weight% based on the combined weight of the polyglycerols, and cyclic
pentaglycerol in
an amount of 2.0 to 5.0 weight% based on the combined weight of the
polyglycerols.
In one preferred aspect the polyglycerol composition used to form the
polyglycerol ester
of a fatty acid comprises a mixture of
10 acyclic
diglyceroi in an amount of 9.0 to 24.5 weight% based on the combined
weight of the polyglycerois, and cyclic diglycerol in an amount of 6.5 to 10.0
weight%
based on the combined weight of the polygiycerols;
acyclic triglycerol in an amount of 9.0 to 20.5 weight% based on the combined
weight of the polyglycerols, and cyclic triglyceroi in an amount of 3.5 to 6.5
weight%
15 based on the combined weight of the polyglycerols;
acyclic tetraglycerol in an amount of 8.0 to 13.5 weight% based on the
combined
weight of the polyglycerols, and cyclic tetraglycerol in an amount of 2.0 to
4.5 weight%
based on the combined weight of the polyglycerols;
acyclic pentaglycerol in an amount of 6.0 to 9.0 weight% based on the combined
20 weight of the polyglycerols, and cyclic pentaglycerol in an amount of
2.0 to 5.0 weight%
based on the combined weight of the polyglycerols;
hexaglycerol in an amount of 7.0 to 11.0 weight% based on the combined weight
of the polyglycerols;
neptaglycerol in an amount of 5.0 to 10.0 weight% based on the combined
weight of the polyglycerols;
octaglycerol in an amount of 3.0 to 9.0 weight% based on the combined weight
of the polyglycerols;
nonaglycerol in an amount of 1.5 to 7.0 weight% based on the combined weight
of the polyglycerols;
decaglycerol in an amount of 0.0 to 4.5 weight% based on the combined weight
of the polyglycerols; and
unadecaglycerol in an amount of 0.0 to 4.0 weight% based on the combined
weight of the polyglycerols.

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In one preferred aspect the poiyglycerol composition used to form the
polyglyceroi ester
of a fatty acid comprises diglycerol in an amount of 26.0 to 34.0 weight%
based on the
combined weight of the polyglycerois. In one preferred aspect the polyglycerol

composition used to form the polyglycerol ester of a fatty acid comprises
trialycerol in an
amount of 21.0 to 25.0 weight% based on the combined weight of the
polyglycerols. tn
one preferred aspect the polyglycerol composition used to form the
poiyglycerol ester of
a fatty acid comprises tetraglycerol in an amount of 12.0 to 17.0 weight%
based on the
combined weight of the polyglycerols. In one preferred aspect the polyglycerol

composition used to form the polyglycerol ester of a fatty acid comprises
pentaglycerol in
an amount of 8.0 to 12.0 weight% based on the combined weight of the
polyglycerols. In
one preferred aspect the polyglycerol composition used to form the
polyglycerol ester of
a fatty acid comprises hexaglycerol in an amount of 6.0 to 10.0 weight% based
on the
combined weight of the polyglycerols. In one preferred aspect the polyglycerol

composition used to form the polyglycerol ester of a fatty acid comprises
heptaglycerol in
an amount of 4.5 to 7.5 weight% based on the combined weight of the
polyglycerols. In
one preferred aspect the polyglycerol composition used to form the
polyglycerol ester of
a fatty acid comprises octaglycerol in an amount of 2.5 to 5.5 weight% based
on the
combined weight of the polyglycerols. In one preferred aspect the poiyglycerol

composition used to form the polyglycerol ester of a fatty acid comprises
nonaglycerol in
an amount of 1.0 to 3.0 weight% based on the combined weight of the
polyglycerols. In
one preferred aspect the polyglycerol composition used to form the
polyglycerol ester of
a fatty acid comprises decaglycerol in an amount of 0.0 to 1.0 weight% based
on the
combined weight of the polyglycerols. In one preferred aspect the polyglycerol

composition used to form the polyglycerol ester of a fatty acid comprises
unadecaglycerol in an amount of 0.0 to 0.5 weight% based on the combined
weight of
the polyglycerols.
In one preferred aspect the polyglycerol composition used to form the
polyglycerol ester
of a fatty acid comprises unadecagiycerol in an amount of 0.0 to 0.01 weight%
based on
the combined weight of the polyglycerols.
In one preferred aspect the polyglycerol composition used to form the
polyglyceroi ester
of a fatty acid comprises a mixture of
diglycerol in an amount of 26.0 to 34.0 weight% based on the combined weight
of the polyglycerols;

CA 02839237 2013-12-12
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22
triglycerol in an amount of 21.0 to 25.0 weight /0 based on the combined
weight of
the polyglycerols;
tetraglycerol in an amount of 12.0 to 17.0 weight% based on the combined
weight
of the polyglycerols;
pentagiycerol in an amount of 8.0 to 12.0 weicht% based on the combined weight
of the polyglycerols;
hexaglycerol in an amount of 6.0 to 10.0 weight% based on the combined weight
of the polyglycerols;
heptaglycerol in an amount of 4.5 to 7.5 weight% based on the combined weight
to of the polyglycerols;
octaglycerol in an amount of 2.5 to 5.5 weight% based on the combined weight
of
the polyglycerols;
nonaglycerol in an amount of 1.0 to 3.0 weight% based on the combined weight
of the poiyglycerols;
decaglycerol in an amount of 0.0 to 1.0 weight% based on the combined weight
of the polyglycerois; and
unadecaglycerol in an amount of 0.0 to 0.5 weight% based on the combined
weight of the polyglycerols.
In one preferred aspect the diglycerol comprises acyclic diglycerol in an
amount of 20.0
to 26.0 weight% based on the combined weight of the polyglycerols, and cyclic
diglycerol
in an amount of 6.5 to 8.0 weight% based on the combined weight of the
polyglycerols.
In one preferred aspect the triglycerol comprises acyclic triglycerol in an
amount of 18.0
to 21.0 weight% based on the combined weight of the polyglycerois, and cyclic
triglycerol
in an amount of 2.5 to 5.0 weight% based on the combined weight of the
polyglycerols.
In one preferred aspect the tetraglycerol comprises acyclic tetraglycerol in
an amount of
11.0 to 14.5 weight% based on the combined weight of the polyglycerols, and
cyclic
tetraglycerol in an amount of 1.5 to 4.0 weight% based on the combined weight
of the
polyglycerols. in one preferred aspect the pentaglycerol comprises acyclic
pentaglycerol
in an amount of 6.5 to 9.5 weight% based on the combined weight of the
polyglycerols,
and cyclic pentaglycerol in an amount of 1.5 to 4.0 weight% based on the
combined
weight of the polyglycerols.
In one preferred aspect the triglycerol comprises acyclic triglycerol in an
amount of 18.0
to 21.0 weight% based on the combined weight of the polyglycerols,

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23
In one preferred aspect in the polyglyceroi composition used to form the
polyglycerol
ester of a fatty acid
the diglycerol comprises acyclic diglycerol in an amount of 20.0 to 26.0
weight%
based on the combined weight of the polyglycerols, and cyclic diglycerol in an
amount of
6.5 to 8.0 weight% based on the combined weight of the polyglycerols;
the triglycerol comprises acyclic triglycerol in an amount of 18.0 to 21.0
weight%
based on the combined weight of the polyglycerols, and cyclic triglycerol in
an amount of
2.5 to 5.0 weight% based on the combined weight of the polyglycerols;
the tetraglycerol comprises acyclic tetraglycerol in an amount of 11.0 to 14.5
weight% based on the combined weight of the polyglycerols, and cycIic
tetraglycerol in
an amount of 1.5 to 4.0 weight% based on the combined weight of the
polyglycerols; and
the pentaglycerol comprises acyclic pentaglycerol in an amount of 6.5 to 9.5
weight% based on the combined weight of the polyglycerols, and cyclic
pentaglycerol in
IS an amount of 1.5 to 4.0 weight% based on the combined weight of the
polyglycerols.
In one preferred aspect the polyglycerol composition used to form the
polyglycerol ester
of a fatty acid comprises a mixture of
acyclic diglycerol in an amount of 20.0 to 26.0 weight% based on the combined
weight of the polyglycerols, and cyclic diglycerol in an amount of 6.5 to 8.0
weight%
based on the combined weight of the polyglycerols;
acyclic triglycerol in an amount of 18.0 to 21.0 weight% based on the combined

weight of the polyglycerols, and cyclic triglycerol in an amount of 2.5 to 5.0
weight%
based on the combined weight of the polyglycerols;
acyclic tetraglycerol in an amount of 11.0 to 14.5 weight% based on the
combined weight of the polyglycerols, and cyclic tetraglycerol in an amount of
1.5 to 4.0
weight% based on the combined weight of the polyglycerols;
acyclic pentaglycerol in an amount of 6.5 to 9.5 weight% based on the combined

weight of the polyglycerols, and cyclic pentaglycerol in an amount of 1.5 to
4.0 weight%
based on the combined weight of the polyglycerols;
hexaglycerol in an amount of 6.0 to 10.0 weight% based on the combined weight
of the polyglycerols;
heptaglycerol in an amount of 4.5 to 7.5 weight% based on the combined weight
of the polyglycerols;

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94
ootagiycerol in an amount of 2.5 to 5.5 weight% based on the combined weight
of
the polygl-ycerois;
nonagiycerol in an amount of 1.0 to 3.0 weight% based on the combined weight
of the po!yglycerols;
decaglycerol in an amount of 0.0 to 1.0 weight% based on the combined weight
of the polyglycerols; and
unadecaglyceroi in an amount of 0.0 to 0.5 weight% based on the combined
weight of the polygiycerols.
The fatty acid side chains attached to the polyglycerol may be of any suitable
length. The
polyglycerol ester of a fatty acid may be a polyglycerol ester of a single
fatty acid, or
poiyglyceroi ester of a mixture of fatty acids. The fatty chain lengths of the
fatty acids of
the polyglycerol ester need not be of the same length. Typically the
polyglycerol ester of
a fatty acid is an ester of a fatty acid of a C12 to C22 fatty acid.
Preferably the
polyglycerol ester of a fatty acid is an ester of a C16 or C22 fatty acid.
Preferably the
polyglycerol ester of a fatty acid is an ester of a C16 or C18 fatty acid.
Preferably the
polyglycerol ester of a fatty acid is an ester of a C18 fatty acid.
The fatty acid of the polyglycerol ester of a fatty acid may be saturated
fatty acid,
unsaturated fatty acid or a mixture of saturated fatty acid and unsaturated
fatty acid. In
one aspect the fatty acid of the polyglycerol ester of a fatty acid is an
unsaturated fatty
acid. The fatty acid of the polyglycerol ester of a fatty acid may be mono- or
di-
unsaturated fatty acid. Preferably the fatty acid of the polyglycerol ester of
a fatty acid is
a mono-unsaturated fatty acid.
A highly preferred fatty acid of the polyglycero! ester of a fatty acid is
oleic acid ((9Z)-
Octadec-9-enoic acid).
The fatty acids attached to the polyglycerol may be provided from any suitable
source.
Thus in one aspect, the polyglycerol fatty acid ester is prepared from fatty
acids from oils
selected from rape seed oil, high oleic rape seed oil, soy oil, high oleic
sunflower oil, tall
oil and mixtures thereof.
In one preferred aspect the polyglycerol composition used to form the
polyglycerol ester
of a fatty acid has a hydroxyl value of from 880 to 1230 mg KOH/g. In one
preferred

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aspect the poiyglycerol composition used to form the polyglycerol ester of a
fatty acid
has a hydroxyl value of from 1130 to 1230 mg In
one preferred aspect the
polyglycerol composition used to form the polyglycerol ester of a fatty acid
has a hydroxyl
value of from 880 to 1060 mg KOH/g. in a further preferred aspect the
polyglycerol
5 composition used to form the polyglycerol ester of a fatty acid has a
hydroxyl value of
from 950 to 990 mg KOH/g.
In one preferred aspect the polyglycerol composition used to form the
polyglycerol ester
of a fatty acid has a refractive index at 50 C of from 1.4860 to 1.4925. in
one preferred
in aspect the polyglycerol composition used to form the polyglycerol ester
of a fatty acid
has a refractive index at 50 C of from 1.4895 to 1.4925. In a further
preferred aspect the
polyglycerol composition used to form the polygiycerol ester of a fatty acid
has a
refractive index at 50 C of from 1.4900 to 1.4920. In a further preferred
aspect the
polyglycerol composition used to form the polyglycerol ester of a fatty acid
has a
15 refractive index at 50 C of from 1.4900 to 1.4910. In one preferred aspect
the
polyglycerol composition used to form the polyglycerol ester of a fatty acid
has a
refractive index at 25 C of from 1.4855 to 1.4935.
In one preferred aspect the polyglycerol ester of a fatty acid has a viscosity
of less than
20 700 mPa s at 20 C, such as less than 600 mPa s at 20 C, such as less
than 500 mPa s
at 20 C, such as less than 400 mPa s at 20 C, such as less than 350 mPa s at
20 C,
such as less than 300 mPa s at 20 C, such as less than 250 mPa s at 20 C, such
as
less than 200 mPa s at 20 C. We have found that during the preparation of a
fuel
emulsion in accordance with the present invention a low viscosity, such as
that described
25 above, and preferably less than 200 mPa s at 20 C, is an important factor
in the
preparation of an effective emulsion.
We have found that a means by which the viscosity the polyglycerol ester of a
fatty acid
may be controlled is by control of the ratio of the polyol to triglyceride
source when
preparing the present polyglycerol ester of a fatty acid, as well as the fatty
acid profile
which is described in detail herein. The effect of ratio of the polyol to
triglyceride source
is shown in Figure 8. Thus in one aspect the polyglycerol ester of a fatty
acid is prepared
by reacting a polyglycerol and a fatty acid triglyceride in a ratio of
polyglycerol to fatty
acid triglyceride of from 1:1 to 1:10. Preferably the polygiycerol ester of a
fatty acid is
prepared by reacting a polyglycerol and a fatty acid triglyceride in a ratio
of polyglycerol

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26
to fatty acid trigiyceride of from 1:1 to 1:9, such as from 1:1 to 1:8, such
as from 1:1 tc
1:7, such as from 1:1 to 1:6, such as from 1:1 to 1:5, such as from 1:1 to
1:4, such as
from 1:2 to 1:4, such as from 1:2 to 1:3, such as approximately 1:2.8, such as
from 1:4 to
1:9, such as from 1:4 to 1:8, such as from 1:4 to 1:7, such as from 1:4 to
1:6, such as
from 1:4 to 1:5, such as from 1:5 to 1:7, such as from 1:6 to 1:7, such as
approximately
1:6.7.
Fuel Composition
When a polyglycerol ester of a fatty acid prepared from a mixture of
polyglycerols as
described herein is provided in accordance with the present invention, the
polyglycerol
ester may be dosed in the water and fuel composition in any suitable amount to
provide
an emulsion of desired stability, in one aspect the fuel composition comprises
a
polyglycerol ester of a fatty acid prepared from a mixture of polyglycerols as
described
herein in an amount of from 0.1 to 2.0 wt.% based on the total fuel
composition. In a
further aspect the fuel composition comprises a polyglycerol ester of a fatty
acid
prepared from a mixture of polyglycerols as described herein in an amount of
from 0.1 to
1.0 wt.% based on the total fuel composition. In a further aspect the fuel
composition
comprises a polyglycerol ester of a fatty acid prepared from a mixture of
polyglycerols as
described herein in an amount of from 0.1 to 0.5 wt.% based on the total fuel
composition. In a further aspect the fuel composition comprises a polyglycerol
ester of a
fatty acid prepared from a mixture of polyglycerols as described herein in an
amount of
less than 0.5 wt.% based on the total fuel composition. In a further aspect
the fuel
composition comprises a polyglycerol ester of a fatty acid prepared from a
mixture of
polyglycerols as described herein in an amount of less than 0.3 wt.% based on
the total
fuel composition, in a further aspect the fuel composition comprises a
polyglycerol ester
of a fatty acid prepared from a mixture of polyglycerois as described herein
in an amount
of less than 0.25 wt.% based on the total fuel composition. In a further
aspect the fuel
composition comprises a polyglycerol ester of a fatty acid prepared from a
mixture of
polyglycerols as described herein in an amount of less than 0.2 wt.% based on
the total
fuel composition. in a further aspect the fuel composition comprises a
polyglycerol ester
of a fatty acid prepared from a mixture of polyglycerois as described herein
in an amount
of less than 0.15 wt.% based on the total fuel composition. In a further
aspect the fuel
composition comprises a polyglycerol ester of a fatty acid prepared from a
mixture of

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27
polyglycerols as described herein in an amount of less than 0.1 wt.% based on
the total
fuel composition.
As discussed herein we have identified that by use of the "flat" composition
of
polyglycerois the emulsifier may be used in lower amounts than required in the
prior art.
Thus in the preferred aspect the polyglycerol ester of a fatty acid is present
in an amount
of less than 0.5 wt.%. The improved activity of the composition of
polyglycerol esters of
the present invention allows for the emulsifier to be dosed at lower amounts
than had
previously been required in the prior art. This is advantageous both for
reasons of cost
and also for storage. These materials are dosed in use and therefore must be
transported by the user. Minimising the amount of material required to achieve
the
desired effect is important for end users. Although the present composition
allows for use
at lower levels than the prior art, the present composition may be dosed at
any level, for
example it may be dosed at a higher level in a demanding application. It is
appreciated
by one skilled in the art that depending on the required use and stability
time desired the
polyglycerol ester of a fatty acid may be dosed at any amount.
Fuel
As discussed herein, the emulsifiers described allow for the preparation of an
emulsion
of fuel and water. A fuel suitable for preparing into an emulsion but which
has yet to be
combined with water is hereby encompassed within the present invention.
However, in a
preferred aspect, the fuel containing the emulsifiers is combined with water
and the fuel
composition further comprises (c) water. it will be appreciated that in this
aspect the fuel
composition may be prepared by first dosing the polyglycerol ester of a fatty
acid into the
fuel, such as marine gasoil (VIGO), after which water is dosed into the
fuel/emulsifier
blend.
The amount of water may be selected based on the requirements of the
combustion
system. In one aspect the fuel composition further comprises (c) water in an
amount of
from 10 to 70 wt.% based on the total fuel composition. Preferably the water
is present in
an amount of from 30 to 60 wt.% based on the total fuel composition.
Preferably the
water is present in an amount of from 33 to 50 wt.% based on the total fuel
composition.

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28
The composition according to the present invention may comprise one or more
additives
for example, to improve various aspects of the fuel to which the composition
is typically
added or to improve various aspects of the combustion system performance.
Suitabie
additional additives include detergents, carrier oils, anti-oxidants,
corrosion inhibitors,
colour stabilisers, metal deactivators, cetane number improvers, other
combustion
improvers, antifoams, pour point depressants, cold filter plugging point
depressants, wax
anti-seftling additives, dispersants, deodorants, dyes, smoke suppressants,
lubricity
agents, and other particulate filter regeneration additives.
io The fuel may be any fuel suitable for combustion where reduction of NOx
is desired. In
one aspect the fuel is a fuel for spark ignition engines such as a gasoline
engine.
Preferably the fuel is a fuel for a high compression spontaneous ignition
engine. In one
aspect the fuel is selected from diesel, heavy fuel oil, marine gasoil (MGO)
and
kerosene. The dies& may be biodiesel, low sulphur diesel and ultra-low sulphur
diesel.
Preferably the fuel is marine gasoil. The marine gasoil may be any suitable
marine
gasoil. In one aspect it is a fuel having a (i) a density of 0.85-0.89g/cm3, a
cetane
Number of approximately 45; and a flash point of greater than 55 C.
Aspects of the invention are defined in the appended claims.
The present invention will now be described in further detail in the following
examples in
which:
Figures 1, 3a, 3b, 7 to 9 and 13 show graphs; and
Figures 2, 3c, 4, 5, 6, 10, 11, 12 and 14 show images.
EXAMPLES
Example 1,
30 Four polygiyceroi esters were prepared and tested. Two were broad range
polyglycerol
(BRPG) esters in accordance with the present invention - one based on soya
bean oil
and one based on oleic acid. Two were triglycerol esters prepared as a
comparison - one
based on soya bean oil and one based on oleic acid.
35 Manufactij.L._.'esjzagliglycer&

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29
Glycerol: 1250 kg
50% NaOH in water: 9.17 kg
Glycerol and NaOH solution is added to the reactor. Heated to 240 C while
taking care
with columns and condensers not to distill off glycerol. The heating to 240 C
takes about
3h. Then the pressure is lowered carefully to about 30 mbar to remove reaction
water
from the polymerisation of glycerol. After about 7-14 hours at 240 C samples
are
withdrawn from the reactor for measurement of refractive index at 50.0 C,
I0
The refractive index is used to determine the termination of the reaction. The
refractive
index should be in the interval of 1.4900-1.4920. If the refractive index is
not yet in the
interval, the reaction is continued for further 1 hour and another sample is
withdrawn for
measurement. This continues until the refractive index is within the interval.
When the
is polyglycerol is within the stop-interval the temperature is lowered to
120 C.
The glycerol and polyglycerol content of the BRPG samples was determined. The
details
of this analysis are given below.
Polyglycerol BRPG BRPG BRPG BRPG
composition Batch 1 Batch 2 Batch 3 Batch 4
(reanalysis in [ ])
%Glycerol 4.81 5.49 4.22 [4.24] 5.15
% CY-Diglycerol 8.68 8.42 9.14 [9.14] 8.13
% Diglycerol 10.04 10.85 8.68 [8.67] 10.58
% CY-Triglycerol 5.94 5.58 6.00 [6.02] 5.70
% Triglycerol 10.57 11.15 9.4719.46] 11.00
A) CV- 4.20 3.90 3.93 [4.24] 4.06
Tetraglycerol
% Tetraglycerol 8.76 9.12 8.00 [8.00] 9.06
% CV- 4.13 3.60 4.44 [4.38] 3.59
Pentaglycerol
% Pentaglycerol 6.95 7.20 6.44 [6.53] 6.40
% Hexaglycerol 9.36 8.98 8.89 [9.22] 9.58
% Heptaglycerol 8.71 8.15 8.63 [8.96] 9.44
% Octaglycerol 7.27 7.02 8.52 [7.57] 7.02
% Nonaglycerol 5.58 5.20 6.07 [5.80] 5.36
% Decaglycerol 3.31 3.51 4.20 [4.25] 2.76
%Undecaglycerol 1.69 1.82 3.38 [3.54] 2.17
Normalised from 95.89 97.02 95.59 [95.06] 98.53
Specifications of the hydroxyl values and the refractive index for the broad
range

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,00lyglyceroi of the present invention and the triglycerol used for the esters
below are
given below:
Broad range polyglyceroi
5 Hydroxyl value (OHV): 950-990
Refractive index at 50 C: 1.4900.-1.4920
Triglycerol
Hydroxyl value (OHV): 1090-1190
10 Refractive index (20 C): 1.4930-1.4970
Manufacture of Tliglycel_L9L_i and Poivq1vcerol esters:
egligiyi cern; PGE 2440/198:
Soyabean oil: 700g
Polyglycerol: 203.2g
50% NaOH in water: 3.80g
The polyglycerol was prepared in accordance with the above process.
All ingredients are charged to a 3-necked flask with mechanical stirring,
condenser,
temperature control, nitrogen protection is used, vacuum pump is connected to
the set-
up.
Temperature is raised to 90 C. Pressure is lowered to about 50 mBar when the
mixture
reaches 90 C. Temperature is then raised to 230 C and held at that temperature
for 30
min. Cooled to about 90 C. Pressure equalised with nitrogen at 90 C. The
product is
clear.
Analysis: Acid value: 0.3; Saponification value: 146.2; Hydroxyl value: 219.2.
Polyglycerol PGE 2526/160:
Oleic acid 90%: 340g

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31
Polyglycerol: 102g
Glycerd: 37g
50% NaOH in water: 1.75g
The polyglycerol was prepared in accordance with the above process.
A!l ingredients are charged to a 3-necked flask with mechanical stirring,
vigreux column,
condenser, temperature control, nitrogen protection is used, vacuum pump is
connected
to the set-up.
Temperature is raised gradually to 235 C. At 208 C reaction water is distilled
off. After
80 min. the mixture is clear and the temperature is 235 C. The reaction
mixture is
reacted for further 1h.
The pressure is lowered gradually to 75 mBar. Then the mixture reacts for
further 1h. A
sample is withdrawn for acid value measurement.
When the acid value is below 2 the product is finished and the temperature is
lowered to
90 C. Pressure equalised with nitrogen. The product is ciear.
Analysis: Acid value: 0.5; Saponification value: 145.5; Hydroxyl value: 214.9;
Alcaline
number: 7.4.
Piggyperoi PGE 2528/072_(ComparativeL
Soyabean oil: 700g
Triglycerol: 215g
50% NaOH in water: 3.80g
The triglycerol was obtained from Solvay.
All ingredients are charged to a 3-necked flask with mechanical stirring,
condenser,
temperature control, nitrogen protection is used, vacuum pump is connected to
the set-
up.

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32
Pressure is lowered to about 50 mBar when the mixture reaches 90 C.
Temperature is
raised from room temperature to 230 C in 85 min. The reaction mixture is held
at 230 C
for 2.5h, then cooled to 90 C and pressure equalised with nitrogen. The
product is clear.
Analysis: Acid value: 0.2; Saponification value: 142.6; Iodine value: 95.2;
Color 5 1/4",
Total: 3.0 yellow: 15 red: 1.5.
Trighover , PGE 2526/159 (Comparative,:
Oleic acid 90%: 340g
Triglycerol: 108g
Glycerol: 37g
50% NaOH in water: 1.75g
The triglycerol was obtained from Solvay.
All ingredients are charged to a 3-necked flask with mechanical stirring,
vigreux column,
condenser, temperature control, nitrogen protection is used, vacuum pump is
connected
to the set-up.
Temperature is raised gradually to 235 C. At 208 C reaction water is observed.
After 65
min. the mixture is clear and the temperature is 235 C. The reaction mixture
is reacted
for further lh. The pressure is lowered gradually to 75 mBar, then the mixture
reacts for
further 1h. A sample is withdrawn for acid value measurement. When the acid
value is
below 2 the product is finished and the temperature is lowered to 90 C.
Pressure
equalised with nitrogen. The product is clear.
Analysis: Acid value: 0.8; Saponification value: 143.6; Hydroxyl value: 262.8;
Alcaline
number: 4.6.
Four polyglycerol esters based on either soy oil or oleic acid and either
triglycerol or
broad range polyglycerol (BRPG) esters were tested in water-in-fuel emulsion
(WIF-
emulsion) with 50% water content at 55 C with focus on water droplet size
distribution,
stability and emulsion viscosity.

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33
The results of the investigations show that BRPG esters provides smaller water
droplets
and reduced water droplet sedimentation during storage compared to triglycerol
esters.
Four samples were tested with two polyol distributions (triglycerol vs. BRPG)
and two
EXPERIMENTAL
content at 55 C. The emulsifiers are listed in table 1. Dosages 0.5%, 0.25%
and 0.1%
based on the emulsion. The emulsions (200 g) were prepared by slowly adding
the water
phase to the fuel (MGO) during homogenization with Ultra Turrex at 20500 rpm
for 64 s.
Both the MGO and the water were heated to 55 C prior to emulsification.
1. Water droplet size distribution by NMR.
2. Microscopy by CLSM.
3. Emulsion stability during 3 hours storage at 55 C by imaging and image
analysis.
./0
Polyglycerol Material Fatty acid Polyglycerol
Type composition %
BRPG 2440/198 soy oil 23.8*
BRPG 2526/160 Oleate 27.0
Triglycerol 2528/072 soy oil 23.8*
Triglycerol 2526/159 Oleate 28.6
Table 1 * The low polyol percentage is due to the fatty acid source.
The marine gasoil (diesel) used in the testing was Shell Thermo heating oil.
25 RESULTS
The water droplet size distribution is shown in Table 2. Note the significant
increase in
water droplet size at low emulsifier concentration.

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34
Emulsifier Conc % Conc % Water % Temp D2.5 D50.0
Emulsion Diesel Emulsion C pm pm
2440/198 0.50 1.00 50 55 0.6 7.7
BR.PG.. soy 0.25 0.50 50 55 3.3 16.6
0.10 0.20 50 55 4.2 63.0
2526/160 0.50 1.00 50 55 0.5 7.1
BRPG - oleate 0.25 0.50 50 55 3.7 18.6
0.10 0.20 50 55 6.7 47.0
2528/072 0.50 1.00 50 55 0.4 6.6
Triglycerol - soy 0.25 0.50 50 55 2.7 17.8
0.10 0.20 50 55 2.8 87.8
2526/159 0.50 1.00 50 55 0.5 7.4
Triglycerol - 0.25 0.50 50 55 1.9 14.9
oleate 0.10 0.20 50 55 4.5 72.7
Table 2 Water droplet size distribution.
The D50.0 values are compared in Figure 1, where the huge increase in droplet
size at
0.1% dosage ievel is clearly seen. The graph also shows that at very stressing
conditions
(0.1% emulsifier dosage) PGE based on BRPG (broad range polyglycerol) results
in
smaller water droplets than PGE based on triglycerol. At the same time PGE
based on
fatty acids from soy oil results in larger droplets than PGE based on pure
oleic acid.
to The droplet size distribution by CLSIVI is seen below with a comparison
between 0.5%
and 0.1% emulsifier dosage. The huge increase in droplet size at low
emulsifier dosage
is clearly seen on the pictures. Pictures of samples with 0.25% emulsifier
addition are
shown in Figure 2. Pictures of samples with 0.1%, 0.25% arid 0.5% emulsifier
addition
are shown in Figure 6.
In Figure 3a, 3b and 3c are shown the degree of water droplet sedimentation in
the
emulsions during 3 hours storage at 55 C with 0.5%, 0.25% and 0.1% emulsifier
addition. The degree of sedimentation is expressed as the free diesel oil on
top of the
samples in percentage of the total samples height. The values were generated
by image
analysis.
The difference in the degree of sedimentation between the dosage levels is to
be noted.
At 0.1% dosage the sedimentation is ten-fold larger than at 0.5% dosage level.
The ester of triglycerol and soy oil performs poorly at low concentration.
Hence the
performance of this emulsifier is more sensitive to dosage reduction compared
to the
broad range polyglycerol ester emulsifiers of the present invention.

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At low concentration the two emulsifiers based on BRPG of the present
invention
perform better than the emulsifiers based on triglycerol. This is in agreement
with the
difference in water droplet size illustrated in Figure 1.
5
Pictures of the samples are available in Figures 4 and 5.
CONCLUSiON
10 it is clearly documented that polyglycerol esters based on broad range
polygiycerois
results in smaller water droplet and reduced water droplet sedimentation
during storage
as compared to polyglycerolesters based on triglycerol. This effect is seen at
very low
emulsifier addition (0.1%) representing stressing conditions, which most like
a real life
situation. Furthermore it is concluded that a fatty acids composition with
high oleic acid
15 content is superior to a composition with high linoleic acid (soy oil)
based on above
attributes.
Example 2
20 Four further polyglycerol esters were prepared and tested. Each was a
broad range
polyglycerol (BRPG) esters in accordance with the present invention and each
was
based on rape seed oii. Two were triglycerol esters and two were hexaglycerol
esters.
The esters in accordance with the present invention were compared against a
25 comparison prepared from triglycerol and soy oil (REF PGE or REF).
EXPERMENTAL
PGE 2680/060 with poivol 13%:
Rapeseed oil: 920g
Broad Range Hexaglycerol (BRHG): 138g
50% NaOH in water: 1.92g

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36
The he,xaglycerol was prepared by polymerisation in the same manner as
described in
Example 1.
All ingredients are charged to a 3-necked flask with mechanical stirring,
condenser,
temperature control, nitrogen protection is used, vacuum pump is connected to
the set-
up.
Pressure is lowered to 50 - 100 mBar when the mixture reaches 235 C and is
clear.
Temperature is raised from room temperature to 235 C in 50 min. The reaction
mixture is
held at 235 C for 2.5h, then cooled to 100 C and pressure equalised with
nitrogen. The
product is clear.
Analysis: Acid value: 0.2; Saponification value: 161.8; Hydroxyl value: 125;
Alcaline
number: 3.9
PGE 2680/065 withfighivi 10%:
Rapeseed oil: 960g
Broad Range Hexaglycerol (BRHG): 106.6g
50% NaOH in water: 2.4g
The hexaglycerol was prepared by polymerisation in the same manner as
described in
Example 1.
Al! ingredients are charged to a 3-necked flask with mechanical stirring,
condenser,
temperature control, nitrogen protection is used, vacuum pump is connected to
the set-
up.
Pressure is lowered to 50 - 100 mBar when the mixture reaches 235 C and is
clear.
Temperature is raised from room temperature to 235 C in 50 min. The reaction
mixture is
held at 235 C for 2.5h, then cooled to 100 C and pressure equalised with
nitrogen. The
product is clear.
Analysis: Acid value: 0.2; Saponification value: 168.6; Hydroxyl value: 100.2;
Alcaline
number: 4.1

CA 02839237 2013-12-12
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37
PGE 2680/062 with polvol 23%:
Rapeseed oil: 450g
Broad Range Trigiycerol (BRTG): 135g
50% NaOH in water: 0.82g
The triglycerol was prepared by polymerisation in the same manner as described
in
Example 1 except the refractive index was at 25 C was changed from 1.4855 to
1.4935.
All ingredients are charged to a 3-necked flask with mechanical stirring,
condenser,
temperature control, nitrogen protection is used, vacuum pump is connected to
the set-
up.
Pressure is lowered to 50 - 100 mBar when the mixture reaches 235 C and is
clear.
Temperature is raised from room temperature to 235 C in 50 min. The reaction
mixture is
held at 235 C for 2.5h, then cooled to 100 C and pressure equalised with
nitrogen. The
product is clear.
Analysis: Acid value: 0.1; Saponification value: 144.9; Hydroxyl value: 241.4;
Alcaline
number: 5.0
PGE 2680/073 with polvoi 13%;
Rapeseed oil: 500g
Broad Range Trig lycerol (BRTG): 75g
50% NaOH in water: 0.8g
The triglycerol was prepared by polymerisation in the same manner as described
in
Example 1 except the refractive index was at 25 C was changed from 1.4855 to
1.4935.
All ingredients are charged to a 3-necked flask with mechanical stirring,
condenser,
temperature control, nitrogen protection is used, vacuum pump is connected to
the set-
up.

CA 02839237 2013-12-12
WO 2013/001064 PCT/EP2012/062713
38
Pressure is lowered to 50 - 100 mBar when the mixture reaches 235 C and is
clear.
Temperature is raised from room temperature to 235 C in 50 min. The reaction
mixture is
held at 235 C for 2.5h, then cooled to 100 C and pressure equalised with
nitrogen. The
product is clear.
Analysis: Acid value: 0.2; Saponification value: 163.9; Hydroxyl value: 147.5;
Alcaline
number: 3.7
Poinq Distribution
The polyol distribution of the polyol used in the preparation of each of
2680/062 and
2680/073 was analysed. The analyses was performed twice and an average taken.
The
results of this analysis are given in Table 3 below.
Average of 2 Polyol % based on
Analysis 1 Analysis 2 Analyses total Polyols
%Glycerol 11.08 10.9998 11.03
`)/0 CY-Diglycerol 6.42 6.37 6.4 7.19%
% Dig lycerol 21.56 21.51 21.54 24.20%
% CY-Triglycerol 2.96 3 2.98 3.35%
% Triglycerol 17.74 17.89 17.8182 20.02%
% CY-Tetraglycerol 1.98 2.06 2.02 2.27%
% Tetraglycerol 11.52 11.79 11.6566 13.10%
% CY-Pentaglycerol 2.78 2.7 2.74 3.08%
% Pentaglycerol 6.8 6.93 6.87 7.72%
% Hexaglycerol 6.53 6.67 6.6 7.42%
% Heptaglycercl 4.84 4.89 4.87 5.47%
% Octaglycerol 3.15 3 3.07 3.45%
% Nonaglycerol 1.9 1.62 1.76 1.98%
% Decaglycerol 0.74 0.58 0.66 0.74%
%Undecaglycerol 0 0 0 0.00%
Table 3 - Polyol duplicate analysis
The polyglycerol esters synthesized are summarised in Table 4. Three types of
polyglycerol were included in series, they were two triglycerols and one
hexaglycerol The
fatty acid source was either soy oil or rape seed oil.
Sample Polyol Wt. % Polyol Oil
type Type
REF PGE Tri 23.8 Soy

CA 02839237 2013-12-12
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PCT/EP2012/062713
39
J26801053 BRHG 19.0 Soy
J 2680/054 BRHG 16.0 rape seed
J 2680/060 BRHG 13.0 rape seed
J 2680/062 = RTG 23.1 rape seed
J 2680/06511 HG 10.0 rape seed
J 2680/073 BRTG 13.0 rape seed
Table 4. BRHG BRTG: Broad range Hexarirl-Glycerol
The difference in polyol composition is shown below
The polyol distribution of samples REF PGE, the BRTG used in the preparation
of
2680/073 and the BRHG used in the preparation of 2680/060 are shown in Table
5.
REF PGE :RTG BRHG
%Glycerol 0.1 11 5.2
% CY-Diglycerol 0 6.4 9
% Diglycerol 27 21.5 9.7
% CY-Triglycerol 2.5 3 5.7
% Triglycerol 44.2 17.8 10.3
% CY-Tetraglycerol 4.1 2 4
% Tetraglycerol 12.4 11.7 8.5
% CY-Pentaglycerol 1.6 2.7 4.1
% Pentaglycerol 4.2 6.9 6.8
% Hexaglycerol 2.5 6,6 9.2
% Heptaglycerol 1.2 4.9 8.5
% Octaglycerol 0 3.1 7
% Nonaglycerol 0 1.8 5.4
% Decaglycerol 0 0.7 3.6
%Undecaglycerol 0 0 3.1
Table 5. polyol distribution of samples
The viscosity of each emulsifier was measured on a Physica Rheometer using the
following setup:
Temp: 60 C to -10 C (1 C/min), Shear rate : 23 1/s, Measuring system: DG26.7
7-
SN711; d=Omm
Selected emulsifiers (REF PGE, J2680/060, J2680/065, J2680/073) were further
tested
in WIF-emulsions with 50% water content at 55 C at 0.1% and 0.2% dosage.
Diesel
quality: MGO.
WIF-samples were prepared as described in Example 1.

CA 02839237 2013-12-12
WO 2013/001064 PCT/EP2012/062713
RESULTS
The droplet size distribution is shown in Table 6 and graphically in Figure 9
for D50.0
5 values. Samples 2680/065 and 2680/073 were not stable enough to allow NMR
measurement.
Sample Dosage D2.5 D50.0 comments
%[lril
REF PGE 0.1 1.6 81.0
J2680/060 0.1 5.3 100.0
J 2680/065 0.1 Too fast
Water sedimentation phase
J 2680/073 0.1
separation
REF PGE 0.2 4.2 19.3
J 2680/060 0.2 7.9 32.6
J 2680/065 0.2 3.7 100.0
J 2680/073 0.2 Water phase
separation
Table 6 water droplet size distribution
to The CLSIVI pictures of the emulsion are shown in Figure 10. The images
were recorded
immediately after emulsification. Samples 2680/065 and 2680/073 both provides
much
bigger water droplets at both emulsifier dosage levels as compared to the
reference
(REF PGE) and 2680/060..
15 The CLSIVI images of Figure 11 show a dramatic increase in the water
droplet size at low
emulsifier dosage for samples 2680/065 and 2680/073 as a sign of reduced
functionality.
Also at 0.2% dosage level, the droplets are clearly larger than for samples
REF PGE and
2680/060.
20 Sedimentation and water phase separation after 1h, 2, and 3h storage at
55 C for
sample 2680/073 are shown in Figure 12. Such pronounced water separation is
unusual
with WIF-emulsions. Sedimentation at rest however is not a problem as a
homogeneous
emulsion will be reformed during flow
25 Images of the emulsions are shown in Figure 14.

CA 02839237 2013-12-12
WO 2013/001064 PCT/EP2012/062713
41
The degree of water droplet sedimentation in the emulsions expressed as the
amount of
free oil on top formed during 3 hours of storage at 55 C is shown in Figure
13.
Ail publications mentioned in the above specification are herein inz;orporated
by
reference. Various modifications and variations of the described methods and
system of
the invention will be apparent to those skilled in the art without departing
from the scope
and spirit of the invention. Although the invention has been described in
connection with
specific preferred embodiments, it should be understood that the invention as
claimed
should not be unduly limited to such specific embodiments. Indeed, various
modifications
of the described modes for carrying out the invention which are obvious to
those skilled
in chemistry or related fields are intended to be within the scope of the
following claims

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Title Date
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(86) PCT Filing Date 2012-06-29
(87) PCT Publication Date 2013-01-03
(85) National Entry 2013-12-12
Dead Application 2017-06-29

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Filing $400.00 2013-12-12
Maintenance Fee - Application - New Act 2 2014-06-30 $100.00 2013-12-12
Maintenance Fee - Application - New Act 3 2015-06-29 $100.00 2015-06-26
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DUPONT NUTRITION BIOSCIENCES APS
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Abstract 2013-12-12 1 73
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Drawings 2013-12-12 12 1,750
Description 2013-12-12 41 4,475
Cover Page 2014-02-04 1 42
PCT 2013-12-12 17 658
Assignment 2013-12-12 4 125
Assignment 2013-12-12 5 143
Prosecution-Amendment 2014-04-07 1 27