U.S. patent application number 10/286530 was filed with the patent office on 2003-08-14 for method.
Invention is credited to Henry, Cyrus Pershing JR., Pinch, David Leonard, Sneddon, Andrea.
Application Number | 20030150153 10/286530 |
Document ID | / |
Family ID | 27256311 |
Filed Date | 2003-08-14 |
United States Patent
Application |
20030150153 |
Kind Code |
A1 |
Henry, Cyrus Pershing JR. ;
et al. |
August 14, 2003 |
Method
Abstract
The present invention provides a method for inhibiting deposit
formation in a fuel at a temperature of from 100 to 335.degree. C.,
the method comprising combining with the fuel a composition
comprising: (i) high temperature antioxidant; and (ii) a deposit
inhibiting compound.
Inventors: |
Henry, Cyrus Pershing JR.;
(Wilmington, DE) ; Pinch, David Leonard; (Wirral,
GB) ; Sneddon, Andrea; (Wirral, GB) |
Correspondence
Address: |
FAY, SHARPE, FAGAN,
MINNICH & McKEE, LLP
Seventh Floor
1100 Superior Avenue
Cleveland
OH
44114-2518
US
|
Family ID: |
27256311 |
Appl. No.: |
10/286530 |
Filed: |
November 1, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60332029 |
Nov 21, 2001 |
|
|
|
Current U.S.
Class: |
44/338 ; 44/339;
44/340; 44/347; 44/375; 44/382 |
Current CPC
Class: |
C10L 1/2412 20130101;
C10L 1/1832 20130101; C10L 1/1855 20130101; C10L 1/2283 20130101;
C10L 1/2608 20130101; C10L 10/04 20130101; C10L 1/2641 20130101;
C10L 1/19 20130101; C10L 1/238 20130101; C10L 1/2633 20130101; C10L
1/143 20130101; C10L 1/2616 20130101; C10L 1/2425 20130101; C10L
1/265 20130101; C10L 1/2383 20130101; C10L 1/223 20130101 |
Class at
Publication: |
44/338 ; 44/339;
44/340; 44/347; 44/375; 44/382 |
International
Class: |
C10L 001/22; C10L
001/26; C10L 001/24 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 2, 2001 |
GB |
GB 0126396.1 |
Feb 21, 2002 |
GB |
GB 0204114.3 |
Claims
1. A method for inhibiting deposit formation in a fuel at a
temperature of from 100 to 335.degree. C., the method comprising
combining with the fuel a composition comprising: (i) high
temperature antioxidant; and (ii) a deposit inhibiting compound
2. A method according to claim 1 wherein the high temperature
antioxidant is a phosphorus-containing antioxidant.
3. A composition comprising: (i) a phosphorus-containing
antioxidant; and (ii) a deposit inhibiting compound
4. The invention according to claim 2 or 3 wherein the
phosphorus-containing antioxidant is an organophosphorus-containing
antioxidant.
5. The invention according to claim 2, 3 or 4 wherein the
phosphorus-containing antioxidant is or is derived from an
organophosphorus acid.
6. The invention according to any one of claims 2 to 5 wherein the
phosphorus-containing antioxidant is or is derived from an ester of
an organophosphorus acid.
7. The invention according to any one of claims 2 to 6 wherein the
organophosphorus acid is selected from phosphorus acid, phosphonous
acid, phosphinous acid, phosphoric acid, phosphonic acid or
phosphinic acid.
8. The invention according to claim 7 wherein the
phosphorus-containing antioxidant is an ester of organophosphorus
acid selected from phosphorus acid, phosphonous acid, phosphinous
acid, phosphoric acid, phosphonic acid or phosphinic acid.
9. The invention according to claim 8 wherein the
phosphorus-containing antioxidant is an ester of a phosphonic
acid.
10. The invention according to any one of claims 2 to 9 wherein the
phosphorus-containing antioxidant is a compound of Formula I or II:
17wherein R.sup.1, R.sup.2 and R.sup.3 are independently selected
from H and hydrocarbyl; and X, Y, and Z are independently selected
from O and S.
11. The invention according to claim 10 wherein at least one of X,
Y or Z is O.
12. The invention according to claim 8 or 9 wherein at least one of
Y and Z is O.
13. The invention according to claim 10, 11 or 12 wherein X is S or
O, Y is O and Z is O.
14. The invention according to any one of claims 10 to 13 wherein
each of X, Y and Z is O.
15. The invention according to claim 10 or 11 wherein at least one
of X, Y or Z is O and wherein at least one of X, Y or Z is S.
16. The invention according to any one of claims 10 to 15 wherein
R.sup.1 is selected from H and hydrocarbon.
17. The invention according to any one of claims 10 to 16 wherein
R.sup.1 is selected from H and C1-15 alkyl.
18. The invention according to any one of claims 10 to 17 wherein
R.sup.1 is H.
19. The invention according to any one of claims 10 to 18 wherein
R.sup.2 and R.sup.3 are independently selected from H and
hydrocarbon groups having from 1 to 50 carbons.
20. The invention according to claim 19 wherein R.sup.2 and R.sup.3
are independently selected from H and hydrocarbon groups having
from 1 to 25 carbons.
21. The invention according to claim 19 wherein R.sup.2 and R.sup.3
are independently selected from H and straight chain alkyl groups
having from 1 to 25 carbons.
22. The invention according to claim 19 wherein R.sup.2 and R.sup.3
are independently straight chain alkyl groups having from 10 to 15
carbons.
23. The invention according to any one of claims 2 to 22 wherein
the phosphorus-containing antioxidant is a compound of Formula l:
18wherein R.sup.1, R.sup.2 and R.sup.3 are independently selected
from H and hydrocarbyl; and X, Y, and Z are independently selected
from O and S.
23. The invention according to claim 23 wherein the antioxidant is
of the formula 19
24. The invention according to any one of claims 2 to 22 wherein
the phosphorus-containing antioxidant is a compound of Formula II:
20wherein R.sup.1, R.sup.2 and R.sup.3 are independently selected
from H and hydrocarbyl; and X, Y, and Z are independently selected
from O and S.
25. The invention according to claim 24 wherein the antioxidant is
tridodecylphosphite.
26. The invention according to any one of claims 1 to 25 wherein
the deposit inhibiting compound is of Formula II Polymer-Q-R (II)
wherein Polymer is a polymeric hydrocarbyl group; wherein Q is an
optional ring system; and wherein R is a group selected from H and
hydrocarbyl.
27. The invention according to claim 26 wherein if R is a
hydrocarbyl group it is free of a carboxylic acid group
(--COOH).
28. The invention according to claim 26 or 27 wherein Q together
with R contains no greater than 2 nitrogens.
29. The invention according to claim 26, 27 or 28 wherein when Q
together with R contains 2 nitrogens each of the nitrogens is a
member of a heterocyclic ring.
30. The invention according to any one of claims 26 to 29 wherein Q
together with R contains only 2 nitrogens and wherein each of the
nitrogens is a member of a heterocyclic ring.
31. The invention according to claim 26, 27 or 28 wherein Q
together with R contains no greater than 1 nitrogen.
32. The invention according to claim 31 wherein Q together with R
contains no greater than 1 basic nitrogen.
33. The invention according to any one of claims 26 to 32 wherein
if R is a hydrocarbyl group it is free of a hydroxyl group
(--OH).
34. The invention according to any one of claims 26 to 33 wherein
the optional ring system Q is present.
35. The invention according to any one of claims 26 to 34 wherein Q
is substituted, preferably Q is substituted with one or more groups
selected from .dbd.O and --OH.
36. The invention according to any one of claims 26 to 35 wherein Q
is an aromatic ring.
37. The invention according to any one of claims 26 to 36 wherein Q
has 4 to 10 members, preferably 4 to 6 members, preferably 5 or 6
members.
38. The invention according to any one of claims 26 to 37 wherein Q
is a carbon ring or a heterocyclic ring containing carbon and one
nitrogen.
39. The invention according to any one of claims 26 to 38 wherein Q
is selected from a ring system of the formula 21wherein A is C or
N, preferably Q is selected from a ring system of the formula
22
40. The invention according to any one of claims 26 to 39 wherein
Polymer is a hydrocarbyl group having from 10 to 200 carbons.
41. The invention according to any one of claims 26 to 40 wherein
Polymer is a branched or straight chain alkyl group, preferably a
branched alkyl group.
42. The invention according to any one of claims 26 to 41 wherein
Polymer is polyisobutene.
43. The invention according to any one of claims 26 to 42 wherein
Polymer has a molecular weight of from 700 to 2300, preferably 800
to 1200.
44. The invention according to any one of the preceding claims
wherein the deposit inhibiting compound is selected from compounds
of the formulae 23wherein PIB is polyisobutene.
45. The invention according to claim 44 wherein PIB is
polyisobutene having a molecular weight of from 1000 to 2300.
46. The invention according to any one of the preceding claims
wherein the composition further comprises a metal deactivator.
47. The invention according to claim 46 wherein the metal
deactivator is selected from N,N'-disalicylidene 1,2-propanediamine
and N,N'-disalicylidene 1,2-cyclohexyldiamine.
48. The invention according to any one of the preceding claims
wherein the composition further comprises a further
antioxidant.
49. A fuel composition comprising (a) a fuel (b) a composition as
defined in any one of the preceding claims.
50. A fuel composition according to claim 49 wherein the fuel is an
aviation fuel.
51. A fuel composition according to claim 49 or 50 wherein the fuel
is JP-8 aviation fuel.
52. Use of a composition as defined in any one of the preceding
claims for (i) the inhibition of oxidation of a fuel composition
comprising the composition and a fuel; and/or (ii) the inhibition
of deposit formation in a fuel composition comprising the
composition and a fuel; and/or (iii) the inhibition of particle
formation from the oxidation product(s) of a fuel; and/or (iv) the
solubilisation of deposits and/or deposit precursors.
53. A method as substantially herein before described with
reference to any one of the Examples.
54. A composition as substantially herein before described with
reference to any one of the Examples.
55. A fuel composition as substantially herein before described
with reference to any one of the Examples.
56. A use as substantially herein before described with reference
to any one of the Examples.
Description
[0001] The present invention relates to a composition comprising a
high temperature antioxidant and a deposit inhibiting compound.
[0002] As discussed in U.S. Pat. No. 5,621,154, turbine combustion
fuel oils i.e. jet fuels, such as JP-4, JP-5, JP-7, JP-8, Jet A,
Jet A-1 and Jet B are ordinarily middle boiling distillates, such
as kerosene or combinations of naphtha and kerosene. Military grade
JP-4, for instance, is used in military aircraft and is a blend of
naphtha and kerosene. Military grades JP-7 and JP-8 are primarily
highly refined kerosenes, as are Jet A and Jet A-1, which are used
for commercial aircraft. Civil grades of jet fuel are defined in
ASTM D1655, DefStan 91-91, and other similar specifications. Such
jet fuel are produced from a variety of sources including crude
oil, oil sands, oil shales, Fischer Tropsch processes and gas to
liquid processes. Refinery processing includes fuels produced by
straight distillation, sometimes processed by chemical sweetening,
or hydrogen processing including hydrocracking operations, and may
contain <1 to 3000 ppm sulphur.
[0003] As discussed in U.S. Pat. No. 5,468,262, the thermal
stability of jet fuel has been recognised as a problem for some
years. High-speed flight necessitates that the heat generated be
dissipated through the fuel i.e. the fuel is purposely preheated
prior to combustion. As aircraft have become more sophisticated
with more electronic components, the heat load has increased and
the fuel must be preheated to a higher temperature to absorb the
energy. This makes the thermal stability of the fuel even more
critical.
[0004] These hydrocarbon jet fuels are known to be subject to
deterioration when in contact with oxygen, either on standing in
air or during pre-combustion heating. Such deterioration is thought
to be due to the presence in the fuel of constituents which undergo
oxidative changes resulting in the formation of non-volatile
resinous substances. In addition, the high temperatures and
oxygen-rich atmospheres in aircraft and engine fuel system
components encourage the degradation of the fuel resulting in
particulate and deposit formation.
[0005] The resinous substances and other deposits plug up the
components leading to operational problems including reduced thrust
and performance anomalies in the augmentor, poor spray patterns and
premature failure of mainburner combustors and problems with fuel
controls. Further, the engine exhaust becomes smoky and sooty and
engine noise increases, both of which are undesirable
characteristics for jet engines.
[0006] The problems of deposition from fuels at elevated
temperatures is not limited to the use of fuels in the extreme
environments encountered in aviation. As discussed in WO-A-99/25793
in some oil fired devices, such as boilers and slow heating
cookers, e.g. of the Aga.TM. type, kerosene oil fuel is passed down
a narrow metal feed pipe to the combustion chamber where it is
burnt. Parts of the pipe are sufficiently near the hot chamber for
them to be heated to significant temperatures, resulting in the
risk of thermal degradation of the fuel in the pipe, especially
with slow feed rates and high residence times in the pipe. This
degradation can form solid deposits which reduce the flow and
ultimately stop it, causing the combustion to stop. To overcome
this manufacturers of such devices have for many years recommended
to their users that at least once each six months such pipe parts
are cleaned of solid deposits of coke or other materials.
[0007] GB 2261441 teaches a fuel composition in the gasoline
boiling range containing a polyoxyalkylene compound and the
reaction product of a polyamine and a hydrocarbyl succinic
acylating agent.
[0008] U.S. Pat. No. 5,601,624 discloses a fuel composition
comprising a fuel and a minor amount of a multifunctional additive
such as a dispersant, corrosion inhibitor or antioxidant. The
additive is the reaction product of an oxygenated amine with a
dicarbonyl compound and a hydrocarbyl or hydrocarbylene amine. e.g.
a polyetheramine, glyoxal and a succinimide.
[0009] U.S. Pat. No. 5,990,056 relates to a lubricant composition
comprising an organo substituted benzophenone and at least one
co-additive such as a lubricant antioxidant, a lubricant
dispersant, or an antiwear additive. The compound is thought to act
as a lubricant base or blend stock, a solubility enhancer or a
deposit reducing agent.
[0010] GB 923190 teaches a synergistic antioxidant mix for use in
organic material. The mix comprises a phosphite ester and a
methylene bis phenol. The use in jet fuel, kerosene, and fuel oil
is disclosed.
[0011] GB 791526 discloses dimethyl-(phenyl)-phosphates (e.g.
dimethyl-(tolyl)-phosphate).
[0012] Use of the compounds in hydrocarbons in the gasoline boiling
range is taught.
[0013] In order to alleviate some of the problems outlined above
and meet certain performance and storage requirements, fuels
including jet fuels often contain additives such as antioxidants,
deposit inhibiting compounds, metal deactivators, corrosion
inhibitors and lubricity improvers. It would be apparent to one
skilled in the art that synergistic combinations of any of these
additives would be desirable.
[0014] Antioxidant additives are used not only in fuel but also in
a range of other substances such as lubricants, plastics and food
products.
[0015] The present invention alleviates the problems of the prior
art.
[0016] The present invention relates to the provision of
combinations, in particular synergistic combinations, of
antioxidants and deposit inhibiting compounds.
[0017] Aspects of the invention are defined in the appended
claims.
[0018] In one aspect the present invention provides a method for
inhibiting deposit formation in a fuel at a temperature of from 100
to 335.degree. C., the method comprising combining with the fuel a
composition comprising: (i) high temperature antioxidant; and (ii)
a deposit inhibiting compound.
[0019] By the term "high temperature antioxidant" it is meant an
antioxidant which may prevent oxidation in a fuel at high
temperature. In particular it is meant an antioxidant which
provides improved antioxidant performance when measured in
accordance with the High Temperature Antioxidant Protocol
below.
[0020] In one aspect the present invention provides a composition
comprising (i) a phosphorus-containing antioxidant; and (ii) a
deposit inhibiting compound
[0021] In one aspect the present invention provides a fuel
composition comprising (a) a fuel (b) a composition as defined
herein.
[0022] In one aspect the present invention provides a use of a
composition as defined herein for
[0023] (i) the inhibition of oxidation of a fuel composition
comprising the composition and a fuel; and/or
[0024] (ii) the inhibition of deposit formation in a fuel
composition comprising the composition and a fuel; and/or
[0025] (iii) the inhibition of particle formation from the
oxidation product(s) of a fuel; and/or
[0026] (iv) the solubilisation of deposits and/or deposit
precursors.
[0027] In one aspect the present invention provides a composition
comprising (i) a phosphorus-containing antioxidant; and (ii) a
deposit inhibiting compound, in an amount or a ratio to produce an
antioxidant and/or deposit inhibitory synergistic effect.
[0028] We have found that the combination of a
phosphorus-containing antioxidant, such as di-dodecyl hydrogen
phosphonate, and a deposit inhibiting compound, such as 2300 ButA
Mannich, act in fuels to inhibit oxidation and/or deposition of
material from fuels at elevated temperatures. The oxidation
products or deposited material may block filters and reduce the
efficiency of an engine in which the fuel is combusted. We have
surprisingly found that the combination of products which form the
present composition act in a synergistic manner to prevent or
inhibit oxidation and/or deposition of material.
[0029] We have found that by the provision of the compositions of
the present invention an anti-oxidant and/or deposit inhibitory
effect may be observed, for example by study using Hot Liquid
Process Simulator (HLPS). The anti-oxidant and/or deposit
inhibitory effect is greater than one would expect from the
anti-oxidant and/or deposit inhibitory effect of each of the
composition components, i.e. the combination of components provides
a synergistic effect.
[0030] Preferred Aspects
[0031] Antioxidant
[0032] As discussed above in one aspect the present invention
provides a method for inhibiting deposit formation in a fuel at a
temperature of from 100 to 335.degree. C., the method comprising
combining with the fuel a composition comprising: (i) high
temperature antioxidant; and (ii) a deposit inhibiting
compound.
[0033] Preferably the high temperature antioxidant of the present
invention is a phosphorus-containing antioxidant.
[0034] Preferably the phosphorus-containing antioxidant is an
organophosphorus-containing antioxidant.
[0035] By the term "organophosphorus-containing anti-oxidant" it is
meant a compound comprising at least P and C and may optionally
comprise one or more other suitable atoms. Examples of such atoms
may include hydrogen, sulphur and oxygen.
[0036] By the term "organophosphorus-containing anti-oxidant" it is
meant a compound containing a C--P bond and/or a C--O--P bond
and/or a C--S--P bond.
[0037] Preferably the phosphorus-containing antioxidant is or is
derived from an organophosphorus acid. Preferably the
organophosphorus acid is selected from phosphorus acid, phosphonous
acid, phosphinous acid, phosphoric acid, phosphonic acid or
phosphinic acid.
[0038] In one preferred aspect the phosphorus-containing
antioxidant is or is derived from an ester of an organophosphorus
acid. Preferably the organophosphorus acid is selected from
phosphorus acid, phosphonous acid, phosphinous acid, phosphoric
acid, phosphonic acid or phosphinic acid.
[0039] In a preferred aspect the phosphorus-containing antioxidant
is an ester of an organophosphorus acid. More preferably the
phosphorus-containing antioxidant is an ester of an
organophosphorus acid selected from phosphorus acid, phosphonous
acid, phosphinous acid, phosphoric acid, phosphonic acid or
phosphinic acid.
[0040] In a highly preferred aspect the phosphorus-containing
antioxidant is or is an ester of a phosphonic acid.
[0041] In a highly preferred aspect the phosphorus-containing
antioxidant is an ester of a phosphonic acid.
[0042] Preferably the phosphorus-containing antioxidant contains a
trivalent or pentavalent phosphorus.
[0043] Preferably the phosphorus-containing antioxidant is a
compound of Formula l: 1
[0044] wherein R.sup.1, R.sup.2 and R.sup.3 are independently
selected from H and hydrocarbyl; and X, Y, and Z are independently
selected from O and S.
[0045] Preferably the phosphorus-containing antioxidant is a
compound of Formula II: 2
[0046] wherein R.sup.1, R.sup.2 and R.sup.3 are independently
selected from H and hydrocarbyl; and X, Y, and Z are independently
selected from O and S.
[0047] In the present specification by the term "hydrocarbyl group"
it is meant a group comprising at least C and H and may optionally
comprise one or more other suitable substituents. Examples of such
substituents may include halo-, alkoxy-, nitro-, a hydrocarbon
group, an N-acyl group, a cyclic group etc. In addition to the
possibility of the substituents being a cyclic group, a combination
of substituents may form a cyclic group. If the hydrocarbyl group
comprises more than one C then those carbons need not necessarily
be linked to each other. For example, at least two of the carbons
may be linked via a suitable element or group. Thus, the
hydrocarbyl group may contain hetero atoms. Suitable hetero atoms
will be apparent to those skilled in the art and include, for
instance, sulphur, nitrogen and oxygen.
[0048] In one preferred embodiment of the present invention, the
hydrocarbyl group is a hydrocarbon group.
[0049] Here the term "hydrocarbon" means any one of an alkyl group,
an alkenyl group, an alkynyl group, an acyl group, which groups may
be linear, branched or cyclic, or an aryl group. The term
hydrocarbon also includes those groups but wherein they have been
optionally substituted. If the hydrocarbon is a branched structure
having substituent(s) thereon, then the substitution may be on
either the hydrocarbon backbone or on the branch; alternatively the
substitutions may be on the hydrocarbon backbone and on the
branch.
[0050] X, Y and Z
[0051] Preferably at least one of X, Y or Z is O.
[0052] Preferably at least one of Y and Z is O.
[0053] Preferably X is S or O, Y is O and Z is O. Thus in a highly
preferred aspect the antioxidant of the present invention is of the
formula 3
[0054] wherein X, R.sup.1, R.sup.2 and R.sup.3 are as defined
above.
[0055] Preferably each of X, Y and Z is O. Thus in a highly
preferred aspect the antioxidant of the present invention is of the
formula 4
[0056] wherein R.sup.1, R.sup.2 and R.sup.3 are as defined
above.
[0057] In one aspect at least one of X, Y or Z is O and wherein at
least one of X, Y or Z is S.
[0058] In one aspect, preferably when the antioxidant is of formula
I X is S. Thus in this aspect the antioxidant of the present
invention is of the formula 5
[0059] wherein Y, Z, R.sup.1, R.sup.2 and R.sup.3 are as defined
above.
[0060] R.sup.1, R.sup.2 and R.sup.3
[0061] As disclosed above R.sup.1, R.sup.2 and R.sup.3 are
independently selected from H and hydrocarbyl.
[0062] Preferably R.sup.1 is selected from H and hydrocarbon.
[0063] Preferably R.sup.1 is selected from H and C.sub.1-30
hydrocarbyl, such as C.sub.1-20 hydrocarbyl, C.sub.1-15
hydrocarbyl, C.sub.1-10 hydrocarbyl, C.sub.1, C.sub.2, C.sub.3, or
C.sub.4 hydrocarbyl.
[0064] Preferably R.sup.1 is selected from H and C.sub.1-30
hydrocarbon, such as C.sub.1-20 hydrocarbon, C.sub.1-15
hydrocarbon, C.sub.1-10 hydrocarbon, C.sub.1, C.sub.2, C.sub.3, or
C.sub.4 hydrocarbon.
[0065] Preferably R.sup.1 is selected from H and C.sub.1-30 alkyl,
such as C.sub.1-20 alkyl, C.sub.1-15 alkyl, C.sub.1-10 alkyl,
C.sub.1, C.sub.2, C.sub.3, or C.sub.4 alkyl.
[0066] Preferably R.sup.1 is selected from H and C.sub.1-10 alkyl,
for example C.sub.1, C.sub.2, C.sub.3, or C.sub.4 alkyl.
[0067] In a highly preferred aspect R.sup.1 is H.
[0068] In some aspects, for example when the compound is formula
II, R.sup.1 is selected from
[0069] H and C.sub.1-100 hydrocarbyl, such as C.sub.1-50
hydrocarbyl, C.sub.1-30 hydrocarbyl, C.sub.1-25 hydrocarbyl,
C.sub.1-20 hydrocarbyl, C.sub.1-15 hydrocarbyl, C.sub.1-12
hydrocarbyl, C.sub.5-25 hydrocarbyl, C.sub.8-20 hydrocarbyl,
C.sub.10-15 hydrocarbyl, C.sub.10, C.sub.11, C.sub.12, C.sub.13, or
C.sub.14 hydrocarbyl.
[0070] H and C.sub.1-100 hydrocarbon, such as C.sub.1-50
hydrocarbon, C.sub.1-30 hydrocarbon, C.sub.1-25 hydrocarbon,
C.sub.1-20 hydrocarbon, C.sub.1-15 hydrocarbon, C.sub.1-12
hydrocarbon, C.sub.5-25 hydrocarbon, C.sub.8-20 hydrocarbon,
C.sub.10-15 hydrocarbon, C.sub.10, C.sub.11, C.sub.12, C.sub.13, or
C.sub.14 hydrocarbon.
[0071] H and C.sub.1-100 alkyl, such as C.sub.1-50 alkyl,
C.sub.1-30 alkyl, C.sub.1-25 alkyl, C.sub.1-20 alkyl, C.sub.1-15
alkyl, C.sub.1-12 alkyl, C.sub.5-25 alkyl, C.sub.8-20 alkyl,
C.sub.10-15 alkyl, C.sub.10, C.sub.11, C.sub.12, C.sub.13, or
C.sub.14 alkyl.
[0072] H and C.sub.1-100 straight chain alkyl, such as C.sub.1-50
alkyl, C.sub.1-30 alkyl, C.sub.1-25 alkyl, C.sub.1-20 alkyl,
C.sub.1-15 alkyl, C.sub.1-12 alkyl, C.sub.5-25 alkyl, C.sub.8-20
alkyl, C.sub.10-15 alkyl, C.sub.10, C.sub.11, C.sub.12, C.sub.13,
or C.sub.14 alkyl.
[0073] In a preferred aspect R.sup.2 and R.sup.3 are independently
selected from H and hydrocarbon groups.
[0074] Preferably R.sup.2 and R.sup.3 are independently selected
from H and C.sub.1-100 hydrocarbyl, such as C.sub.1-50 hydrocarbyl,
C.sub.1-30 hydrocarbyl, C.sub.1-25 hydrocarbyl, C.sub.1-20
hydrocarbyl, C.sub.1-15 hydrocarbyl, C.sub.1-12 hydrocarbyl,
C.sub.5-25 hydrocarbyl, C.sub.8-20 hydrocarbyl, C.sub.10-15
hydrocarbyl, C.sub.10, C.sub.11, C.sub.12, C.sub.13, or C.sub.14
hydrocarbyl.
[0075] Preferably R.sup.2 and R.sup.3 are independently selected
from H and C.sub.1-100 hydrocarbon, such as C.sub.1-50 hydrocarbon,
C.sub.1-30 hydrocarbon, C.sub.1-25 hydrocarbon, C.sub.1-20
hydrocarbon, C.sub.1-15 hydrocarbon, C.sub.1-12 hydrocarbon,
C.sub.5-25 hydrocarbon, C.sub.8-20 hydrocarbon, C.sub.10-15
hydrocarbon, C.sub.10, C.sub.11, C.sub.12, C.sub.13, or C.sub.14
hydrocarbon.
[0076] Preferably R.sup.2 and R.sup.3 are independently selected
from H and C.sub.1-100 alkyl, such as C.sub.1-50 alkyl, C.sub.1-30
alkyl, C.sub.1-25 alkyl, C.sub.1-20 alkyl, C.sub.1-15 alkyl,
C.sub.1-12 alkyl, C.sub.5-25 alkyl, C.sub.8-20 alkyl, C.sub.10-15
alkyl, C.sub.10, C.sub.11, C.sub.12, C.sub.13, or C.sub.14
alkyl.
[0077] Preferably R.sup.2 and R.sup.3 are independently selected
from H and C.sub.1-100 straight chain alkyl, such as C.sub.1-50
alkyl, C.sub.1-30 alkyl, C.sub.1-25 alkyl, C.sub.1-20 alkyl,
C.sub.1-15 alkyl, C.sub.1-12 alkyl, C.sub.5-25 alkyl, C.sub.8-20
alkyl, C.sub.10-15 alkyl, C.sub.10, C.sub.11, C.sub.12, C.sub.13,
or C.sub.14 alkyl.
[0078] In a highly preferred aspect the antioxidant is of the
formula 6
[0079] wherein n and m are independently selected from 1 to 15,
preferably 5 to 15, preferably 7 to 13, preferably 8 to 12,
preferably 9, 10 or 11.
[0080] In a highly preferred aspect the antioxidant is of the
formula 7
[0081] This compound is commonly known as di-dodecyl hydrogen
phosphonate.
[0082] In a highly preferred aspect the antioxidant is of the
formula 8
[0083] This compound is commonly known as tridodecylphosphite.
[0084] Deposit Inhibiting Compound
[0085] Preferably the deposit inhibiting compound is of Formula
II
Polymer-Q-R (II)
[0086] wherein Polymer is a polymeric hydrocarbyl group; wherein Q
is an optional ring system; and wherein R is a group selected from
H and hydrocarbyl.
[0087] R
[0088] In one aspect if R is a hydrocarbyl group it is free of a
carboxylic acid group (--COOH).
[0089] In one aspect if R is a hydrocarbyl group it is free of a
hydroxyl group (--OH).
[0090] In one aspect R is selected from H and a nitrogenous
hydrocarbyl group.
[0091] In one aspect R is a nitrogenous hydrocarbyl group.
[0092] The term "nitrogenous hydrocarbyl group" as used herein
means a group comprising at least C, H and N and may optionally
comprise one or more other suitable substituents. Examples of such
substituents may include halo-, alkoxy-, an alkyl group, a cyclic
group etc. In addition to the possibility of the substituents being
a cyclic group, a combination of substituents may form a cyclic
group. If the nitrogenous hydrocarbyl group comprises more than one
C then those carbons need not necessarily be linked to each other.
For example, at least two of the carbons may be linked via a
suitable element or group. Thus, the nitrogenous hydrocarbyl group
may contain hetero atoms. Suitable hetero atoms will be apparent to
those skilled in the art and include, for instance, sulphur.
[0093] In one preferred embodiment of the present invention, the
nitrogenous hydrocarbyl group is a nitrogenous hydrocarbon
group.
[0094] Here the term "nitrogenous hydrocarbon group" means a group
containing only C, H and N (with the proviso of course that Q
together with R contains no greater than 2 nitrogen) including
primary, secondary and tertiary amines, which group may be linear,
branched or cyclic. The term nitrogenous hydrocarbon group also
includes groups which have been optionally substituted. If the
nitrogenous hydrocarbon group is a branched structure having
substituent(s) thereon, then the substitution may be on either the
hydrocarbon backbone or on the branch; alternatively the
substitutions may be on the hydrocarbon backbone and on the
branch.
[0095] Preferably the combined total of nitrogen and carbon atoms
in the nitrogenous hydrocarbon group is from 1 to 10, preferably
from 2 to 8, preferably 2 to 6, for example 2, 4 or 6. Preferably
in this aspect the nitrogenous hydrocarbon group is a straight
chain.
[0096] Q
[0097] Q is an optional ring system. In one aspect the optional
ring system Q is present.
[0098] In one aspect Q is substituted. Preferably Q is substituted
with one or more groups selected from .dbd.O and --OH.
[0099] In one preferred aspect Q is an aromatic ring.
[0100] In one preferred aspect Q has 4 to 10 members, preferably 4
to 6 members, preferably 5 or 6 members.
[0101] Q may be heterocyclic ring or may contain only carbon. The
ring may be a hydrocarbyl ring. In the present specification by the
term "hydrocarbyl ring" it is meant a cyclic group comprising at
least C and H and may optionally comprise one or more other
suitable ring members. Suitable ring members will be apparent to
those skilled in the art and include, for instance, sulphur, and
nitrogen.
[0102] In one preferred aspect Q is a carbon ring or a heterocyclic
ring containing carbon and one nitrogen.
[0103] In one aspect Q is selected from a ring system of the
formula 9
[0104] wherein A is C or N and n is an integer from 1 to 5. In this
aspect preferably Q is selected from a ring system of the formula
10
[0105] wherein A is C or N, i.e. n is 1 or 2.
[0106] In one aspect Q contains an imide group, namely a group of
the formula 11
[0107] Preferably Q is a ring system of the formula 12
[0108] In one aspect Q is a hydrocarbon ring substituted with at
least one alcohol group. The hydrocarbon ring may be aromatic and
in a preferred aspect is a six membered aromatic ring. Preferably Q
is a ring system of the formula 13
[0109] In one aspect Q together with R is a Mannich group or is
derived from or derivable from a Mannich reaction.
[0110] When the ring Q contains a nitrogen, preferably group R is
attached to ring Q via the nitrogen. In other words, the nitrogen
of group Q may be substituted by group R.
[0111] R & Q
[0112] In one aspect Q together with R contains no greater than 2
nitrogens.
[0113] In one aspect when Q together with R contains 2 nitrogens
each of the nitrogens is a member of a heterocyclic ring.
[0114] In one aspect Q together with R contains only 2 nitrogens
and wherein each of the nitrogens is a member of a heterocyclic
ring.
[0115] In one aspect Q together with R contains no greater than 1
nitrogen.
[0116] In one aspect Q together with R contains no greater than 1
basic nitrogen.
[0117] Polymer
[0118] Preferably Polymer is a hydrocarbyl group having from 10 to
200 carbons.
[0119] Preferably Polymer is a branched or straight chain alkyl
group, preferably a branched alkyl group.
[0120] Preferably Polymer has a molecular weight of from 700 to
2500, preferably 1000 to 2300, preferably approximately 1000 or
approximately 2300.
[0121] Preferably Polymer is polyisobutene (PIB). Conventional PIBs
and so-called "high-reactivity" PIBs (see for example EP 0565285)
are suitable for use in the invention. High reactivity in this
context is defined as a PIB wherein at least 50%, preferably 70% or
more, of the terminal olefinic double bonds are of the vinylidene
type.
[0122] Preferably Polymer is polyisobutene having a molecular
weight of from 700 to 2500, preferably 1000 to 2300, preferably
approximately 1000 or approximately 2300.
[0123] In a highly preferred aspect the deposit inhibiting compound
is selected from compounds of the formulae 14
[0124] wherein PIB is polyisobutene.
[0125] In a highly preferred aspect the deposit inhibiting compound
is selected from compounds of the formulae 15
[0126] wherein PIB is polyisobutene having a molecular weight of
approximately 2300
[0127] wherein PIB is polyisobutene having a molecular weight of
approximately 1000
[0128] 1000 ButA PIBamine 16
[0129] wherein PIB is polyisobutene having a molecular weight of
approximately 1000
[0130] 1000 ButA PIBSI
[0131] Composition
[0132] In a preferred aspect the deposit inhibiting compound is
provided in the composition to provide a fuel treat rate of 1-500
mg/l active concentration, preferably 50-300 mg/l, preferably
50-150 mg/l, preferably 75-125 mg/l, preferably approximately 100
mg/l.
[0133] In a preferred aspect the antioxidant is provided in the
composition to provide a fuel treat rate of 1-100 mg/l active
concentration, preferably 5-80 mg/l, preferably 5-50 mg/l
preferably 5-20 mg/l , preferably 7-15 mg/l, preferably 10-13
mg/l.
[0134] In a preferred aspect the composition further comprises a
metal deactivator. Preferably the metal deactivator is
N,N'-disalicylidene 1,2-propanediamine or N,N'-disalicylidene
1,2-cyclohexyldiamine.
[0135] In a preferred aspect the metal deactivator is provided in
the composition to provide a fuel treat rate of 1-50 mg/l active
concentration, preferably 1-30 mg/l, preferably 1-20 mg/l,
preferably 1-10 mg/l, preferably 1-5 mg/l, preferably approximately
2 mg/l.
[0136] In a preferred aspect the composition further comprises a
further antioxidant. A possible further antioxidant is BHT
(2,6-di-t-butyl-4-methyl phenol) or other aviation approved
hindered phenol antioxidants. The additional antioxidants may be
added in order to protect fuel from the build up peroxides on
storage. In a preferred aspect the further antioxidant is provided
in the composition to provide a fuel treat rate 0-100 mg/l,
preferably 5-80 mg/l, preferably 10-50 mg/l, preferably 10-30 mg/l,
preferably approximately 25 mg/l.
[0137] Fuel Composition
[0138] In one aspect the present invention provides a fuel
composition comprising (a) a fuel (b) a composition comprising (i)
a phosphorus-containing antioxidant; and (ii) a deposit inhibiting
compound
[0139] Preferably the fuel is an aviation turbine fuel.
[0140] Preferably the fuel is JP-8 aviation fuel.
[0141] The deposit inhibiting compound may be present in the
composition in amount of at least 1 mg/l or at least 5 mg/l, such
as 1 to 1000, 5 to 1000 for example 5 to 500, 5 to 200 or 10 to 100
mg/l active ingredient based on the weight of the composition e.g.
the fuel composition. The additive may be mixed with the jet or
other fuel composition in the form of a concentrate in solution,
e.g. in an aliphatic aromatic hydrocarbon in 20-80% w/w solution,
or it may be added as such to give a solution in the fuel.
[0142] The composition can comprise jet fuel. The composition can
comprise kerosene, in particular in jet fuel. The main component of
the jet fuel itself is usually a middle boiling distillate boiling
point in the range 150-300.degree. C. at atmospheric pressure and
the fuel is usually kerosene which may be mixed with gasoline
(naphtha) and optionally light petroleum distillate as in mixtures
of gasoline and kerosene. The jet fuel may comprise mixtures of
gasoline and light petroleum distillate, e.g. in weight amounts of
20-80:80-20 such as 50-75:50-25 which weight amounts may also be
used for mixtures of gasoline and kerosene. The jet fuels for
military use are designated JP-4 to 8 e.g. JP-4 as 65% gasoline/35%
light petroleum distillate (according to US Mil. Spec. (MIL
5624G)), JP-5, similar to JP-4 but of higher flash point, JP-7, a
high flash point special kerosene for advanced supersonic aircraft
and JP-8, a kerosene similar to Jet AI (according to MIL 83133C).
Jet fuel for civilian use is usually a kerosene type fuel and
designated Jet A or Jet AI. The jet fuel may have a boiling point
of 66-343.degree. C. or 66-316.degree. C. (150-650.degree. F. e.g.
150-600.degree. F.), initial boiling point of 149-221.degree. C.,
e.g. 204 C. (300-430.degree. F., e.g. 400.degree. F.), a 50%
boiling point of 221-316.degree. C. (430-600.degree. F.) and a 90%
boiling point of 260-343.degree. C. (500-650.degree. F.) and API
Gravity of 30-40. Jet fuel for turbojet use may boil at
93-260.degree. C. (200-500.degree. F.) (ASTM D1655-006). Further
details on aviation fuels may be obtained from "Handbook of
Aviation Fuel Properties", Co-ordinating Research Council Inc., CRC
Report No. 530 (Society of Automotive Engineers Inc., Warrendale,
Pa., USA, 1983) and on US military fuels, from "Military
Specification for Aviation Turbine Fuels", MIL-T-5624P.
[0143] The jet fuel may be the straight run kerosene optionally
with added gasoline (naphtha), but frequently has been purified to
reduce its content of components contributing to or encouraging
formation of coloured products and/or precipitates.
[0144] Among such components are aromatics, olefins, mercaptans,
phenols and various nitrogen compounds. Thus the fuels may be
purified to reduce their mercaptan content e.g. Merox fuels and
copper sweetened fuels or to reduce their sulphur content e.g.
hydrogen treated fuels or Merifined fuels. Merox fuels are made by
oxidation of the mercaptans and have a low mercaptan S content
(e.g. less than 0.005% wt S) such as 0.0001-0.005% but a higher
disulphide S content (e.g. at most 0.4% or at most 0.3% wt S such
as 0.05-0.25 e.g. 0.1-2%); their aromatic (e.g. phenolics) and
olefins content are hardly changed. Hydrogen processed jet fuels
are ones in which the original fuel has been hydrogenated to remove
at least some of sulphur compounds e.g. thiols and under severe
conditions to saturate the aromatics and olefins; hydrofined jet
fuels have very low sulphur contents (e.g. less than 0.01% S by
weight). Merifined fuels are fuels that have been extracted with an
organic extractant to reduce or remove their contents of sulphur
compounds and/or phenols. The jet fuel may also contain metals,
either following contact with metal pipes or carried over from the
crude oil, oil sands, shale oil or sources; examples of such metals
are copper, nickel, iron and chromium usually in amounts of less
than 1 ppm e.g. each in 10-150 ppb amounts. Merox, straight run and
hydrogen processed are preferred and may be used in JP- 4-8 jet
fuels.
[0145] The fuel comprising kerosene may also be a fuel for
combustion especially for non motive purposes, e.g. power
generation, steam generation, and heating, especially for use in
buildings and for cooking, e.g. as described above. The fuel is
particularly suitable for the devices e.g. boilers and slow cookers
as described above in which there is localised preheating of the
fuel before it is combusted.
[0146] Such fuels are known as burning kerosene and may have the
same physical properties as the kerosene based jet fuels described
above, e.g. straight run kerosene, or kerosene modified to reduce
its content of at least one of aromatics, olefins and sulphur
compounds, as described above. The fuel may also contain metals as
described above.
[0147] The fuel compositions of the invention contains the deposit
inhibiting compound and may also contain at least one conventional
additive e.g. for jet fuels or burning fuels such as an
antioxidant, corrosion inhibitor, lubricity improvers, metal
deactivators (MDA), leak detection additives, "special purpose"
additives such as drag reducing agents, anti-icing additives and
static dissipaters such as Stadis.RTM., especially in amounts each
of 1-2000 ppm.
[0148] The use or method of the present invention is typically
performed when the fuel or fuel composition is at a temperature of
no greater than 1100.degree. F. The fuel or fuel composition is
typically at a temperature of 325 to 425.degree. F. during use. In
a one aspect the use or method of the present invention is
preferably performed when the fuel or fuel composition is at a
temperature of from 100 to 335.degree. C.
[0149] The present invention will now be described in further
detail by way of example only with reference to the accompanying
figures in which:--
[0150] FIG. 1 shows HLPS apparatus.
[0151] The present invention will now be described in further
detail in the following examples.
EXAMPLES
[0152] The additives discussed below were tested for HLPS data. The
Protocol for this test is given below.
HLPS Protocol
[0153] Scope--HLPS is a self-contained testing apparatus designed
to test the thermal properties of base and additised jet fuels. The
test involves the flow of the test fuel over a heated test surface
(@335.degree. C.) under high pressure (500 psi).
[0154] Summary--The HLPS is run in accordance with ASTM D-3241. The
conditions for testing are set to those used by the USAF in
extensive thermal stability programmes.
[0155] The basic principles of the HLPS are shown in FIG. 1. As
shown in FIG. 1, 1 litre of test fuel is pressurised in a stainless
steel reservoir to 500 psi. The fuel is then pumped via a
pre-filter over a heated test section (@335.degree. C.). As
deposition occurs on both the tube and in the fuel bulk the bulk
deposit is measured as a filter drop change across a 17 micron
filter. A pressure transducer cell measures the rate of pressure
drop (in mmHg min-1). Finally the spent fuel is returned to the top
of the reservoir, separated by an appropriate seal.
[0156] Apparatus--Alcor HLPS--is a modular version of the equipment
set up as defined in ASTM D-3241. The test section must be of
stainless steel 316 and free from grease. The filter to be used
must be of 17 micron mesh as supplied by Alcor.
[0157] Materials
[0158] Base fuels--are fuels free of additives
[0159] Main Test Procedure
[0160] Sample Preparation
[0161] 1. Filter 1 litre of base test fuel through a 0.7 micron
filter.
[0162] 2. If fuel is to be additised transfer the known weight of
additive(s) to a 1 litre volumetric flask using base test fuel.
[0163] 3. Transfer the test fuel to a 2 litre beaker. Aerate using
the glass bubbler attachment for a minimum of 6 minutes. Test run
must be initiated within 1 hour of aeration.
[0164] 4. Transfer the test fuel to the stainless steel
reservoir.
[0165] 5. Check the piston seal for degradation. If OK place the
piston head on the surface of the fuel and push down using the
supplied handle until fuel begins to seep up from the
reservoir.
[0166] 6. Place the large `O` ring seal in the reservoir top and
secure to the top of the reservoir using a socket wrench.
[0167] 7. Connect the connector tube from the filter unit to the
test cell using new `O` ring.
[0168] 8. Connect all remaining pipe-work using new `O` rings.
[0169] Main Test Run Procedure.
[0170] 1. Close BLEED valve on front of HLPS and open PRESSURISE
valve. Ensure that system is pressurised to 500 psi.
[0171] 2. Ensure that lower knob on delta P cell is turned to
BYPASS and upper knob is VENT CLOSED.
[0172] 3. Switch on PUMP. Red indicator light will come on. Ensure
that FUEL FLOW CONTROL is set to 230. This equates to a flow rate
of 3 mls/min.
[0173] 4. Allow fuel to pump round system until a steady drop rate
is seen through the Perspex window on top of the fuel reservoir.
When steady count the time taken for 20 drops. If the time is 9
seconds.+-.1 seconds this is acceptable for 3 mls/min.
[0174] 5. Ensure that HEATER TUBE TEMP. CONTROL is set to 335 deg.
C. Switch on HEATER. Red indicator light will come on. Needle will
then rise to the vertical. Heater power is controlled by using the
POWER CONTROL dial. A typical setting for this procedure is
82.+-.10 volts.
[0175] 6. Switch on the differential pressure module (DPM) by
depressing the POWER button.
[0176] 7. When needle reads correct temperature switch the delta P
lower knob to RUN. This will divert the fuel flow through the
differential pressure cell.
[0177] 8. Allow the pressure read out on the differential pressure
module to equilibrate and press RECORD. The differential pressure
will be recorded every 5 minutes on the in-built printer.
[0178] 9. Allow the test to run whilst monitoring the differential
pressure change. The DPM has an alarm setting that will cause
multi-point printing at 125 mmHg. If the differential pressure
rises above 300 mmHg turn the lower DPM knob to bypass and note the
time.
[0179] 10. In all cases allow the test run to complete a 5 hour
test sequence. The HLPS will shut down automatically after 5
hours.
[0180] Analysis--Analysis is carried out on the Leco Carbon
Analyser RC412.
[0181] Results--Are quoted for 2 readings.
[0182] Filter blockage--Record the change in differential pressure
during the run. Results are quoted in mmHg min-1, e.g. 300/45,
0/300. The first figure is the change in differential pressure in
mmHg the latter the time in minutes
[0183] Carbon deposit weight--Record the value in
.mu.gcm.sup.-2
High Temperature Antioxidant Protocol
[0184] A high temperature antioxidant candidate is formulated in a
composition comprising the high temperature antioxidant candidate,
2300 ButA Mannich (a deposit inhibiting compound) and
N,N'-disalicylidene 1,2-propanediamine (an MDA). The composition is
dosed into at least three test fuels at a treat rate for each fuel
of
[0185] (i) 100 mg 2300 ButA Mannich per litre of fuel;
[0186] (ii) 0.032 mmoles high temperature antioxidant candidate per
litre of fuel; and
[0187] (iii) 2 mg N,N'-disalicylidene 1,2-propanediamine per litre
of fuel
[0188] Each dosed fuel is subjected to HPLS testing in accordance
with the above Protocol.
[0189] The currently approved stabiliser package SpecAid 8Q462
(available from Shell Aviation as AeroShell Performance Additive
101) is dosed into the same base fuels at a treat rate 256 mg/l for
each fuel. Each dosed fuel is subjected to HPLS testing in
accordance with the above Protocol.
[0190] The pressure drop of each fuel containing the candidate and
the pressure drop of each fuel containing SpecAid 8Q462 is
recorded.
[0191] The pressure drop recorded for the candidate composition in
a given fuel is compared to pressure drop recorded for SpecAid
8Q462 in the same fuel. A candidate is considered to "pass" if for
each fuel the pressure drop recorded for the candidate composition
is no greater than 2 mmHg more than the pressure drop recorded for
SpecAid 8Q462.
[0192] The carbon deposit weight of each fuel containing the
candidate composition and the carbon deposit weight of each fuel
containing SpecAid 8Q462 is recorded. The carbon deposit weight for
the candidate composition is averaged across the number of fuels
tested. The carbon deposit weight for SpecAid 8Q462 is averaged
across the number of fuels tested. A candidate is considered to
"pass" if the average carbon deposit weight for the candidate
composition is less than, equal to or no greater than 10 mg more
than the average carbon deposit weight for the SpecAid 8Q462.
[0193] A candidate which "passes" in respect of both pressure drop
and carbon deposit weight constitutes a "high temperature
antioxidant" within the scope of the present invention.
[0194] The at least three test fuels may be selected from Shell HT,
POSF 3684 (USAF B), Phillips HT, Sunoco, Shell Merox, USAF A, BP
Air Merox, Marathon HT, and Phillips Merox. In one aspect of this
protocol the candidate composition is dosed into POSF 3684 (USAF
B), Phillips HT, Sunoco, Shell Merox, USAF A, BP Air Merox, and
Phillips Merox. In one aspect of this protocol the candidate
composition is dosed into Shell HT, POSF 3684 (USAF B), Phillips
HT, Sunoco, Shell Merox, USAF A, BP Air Merox, Marathon HT, and
Phillips Merox.
[0195] Syntheses
[0196] PIBSIs
[0197] 1000/Butylamine PIBSI
[0198] 1000 mwt high reactive PIB derived PIBSA (467.6 g) was
stirred with Shellsol AB (311.8 g) in a 1 l oil jacketed reactor
equipped with an overhead stirrer, thermometer and Dean & Stark
trap. Whilst still at room temperature butylamine (31.5 g) was
added in one aliquot with continued stirring. An immediate exotherm
was noted. The reaction mix was heated to .about.150.degree. C. for
three hours whilst removing water. 720 g of product was
isolated.
[0199] Analysis of the product showed it to contain 40% m/m
solvent, 0.81% m/m nitrogen.
[0200] 1000 ButA PlBamine
[0201] PIB chloride (153 g, chlorine content 4.89% m/m) was placed
in a stirred reactor with butylamine (61.6 g) and Shellsol (50 ml.
The reactor contents were heated to reflux for 19.5 hours.
Crystalline solid could be seen in the solution as the reaction
proceeded. The reaction was allowed to cool and an excess of
aqueous sodium carbonate was mixed with the reactor contents. After
separation the organics were washed with water and dried over
sodium sulphate. The unreacted butylamine was removed under reduced
pressure leaving the 190 g product plus solvent.
[0202] Analysis of the product showed it to contain 23% m/m
solvent, 0.95% m/m nitrogen, 1% m/m residual chlorine.
[0203] Mannich Compounds
[0204] The Mannichs for use in the present invention may be
synthesised in accordance with the teaching of EP 0831141.
[0205] Results
[0206] The following data were obtained.
[0207] HLPS testing was performed and data collected. Results given
are surface carbon deposit weight (.mu.gcm.sup.-2) and filter
blockage, .DELTA.P, (mmHg/min). A result of 0/300 means that no
blockage has occurred over the 300 minutes of the test, a result of
300/101 means that the filter has completely blocked in 101
minutes.
[0208] The following antioxidants/antioxidant compositions were
used in the Examples
1 AO1 2,6-di-t-butyl-4-methyl phenol AO2
Octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl) propionate AO3
Methylene bis (dibutylthiocarbamate) AO4 2,2'thiodiethyl
bis-(3,5-di-t-butyl-4-hydroxyphenyl) propionate AO5 commercially
available alkylated phenol AO6 3,5-bis-(1,1-dimethyl-ethyl)-4-hydr-
oxybenzenepropanoic ester of C.sub.14-15 alcohol AO7 "synergistic
blend of an aminic and a phenolic antioxidant" AO8 di-dodecyl
hydrogen phosphonate AO9 SpecAid 8Q462 AO10 dioleyl
hydrogenophosphite AO11 tridodecylphosphite AO12
trinonylphenylphosphite AO13 di-n-octylphosphite AO14 isodecyl
diphenylphosphite AO15 butylated triphenyl phosphorothioate AO16
ethyl-3-((bis(1-methylethoxy)phosphinothiony- l)thio)propionate
AO17 ascorbyl palmitate AO18 tocopherol
Example 1
[0209] Assessment of Different Antioxidants in Two Fuels
[0210] A number of different antioxidants/antioxidant compositions
were assessed in two basefuels in a package containing a ButA
Mannich detergent and a MDA. The results were compared against the
fuel, MDA and detergent alone or in various combinations. The HLPS
data are given below.
2 Shell HT POSF 3684 (USAF B) Carbon Carbon Composition
.mu.gcm.sup.-2 .DELTA.P .mu.gcm.sup.-2 .DELTA.P Basefuel 39 300/230
125 300/45 Basefuel + detergent 38 0/300 90.5 12/300 Basefuel + MDA
62 0/300 24 300/101 Basefuel, detergent + MDA 39 0/300 29.5 5/300
Basefuel, detergent, MDA + AO1 (25 mg/l) 41.5 0/300 27 0/300
Basefuel, detergent, MDA + AO2 (60.3 mg/l) 18 0/300 32 1/300
Basefuel, detergent, MDA + AO3 (50 mg/l) 66 0/300 32 4/300
Basefuel, detergent, MDA + AO4 (45 mg/l) 60 0/300 34 0/300
Basefuel, detergent, MDA + AO5 (25 mg/l) 19 300/270 19 9/300
Basefuel, detergent, MDA + AO6 (60 mg/l) 47 6/300 32 6/300
Basefuel, detergent, MDA + AO7 (50 mg/l) 40.3 4/300 28.4 300/26
Basefuel, detergent, MDA + AO8 (13.7 mg/l) 6 0/300 7 0/300
Basefuel, detergent, MDA + AO8 (5 mg/l) 26 0/300 -- -- Basefuel,
detergent, MDA, AO8 (5 mg/l) + AO1 15 1/300 -- -- (25 m/l)
Basefuel, detergent, MDA, AO8 (5 mg/l) + AO2 23 0/300 -- -- (60
mg/l) Basefuel, detergent, MDA, AO8 (13.7 mg/l) + 13 0/300 -- --
AO2 (60 mg/l) Basefuel + AO9 (256 mg/l) 10 0/300 19 0/300 Basefuel,
detergent, MDA + AO10 (21 mg/l) 8 0/300 17 4/300 Basefuel,
detergent, MDA + AO11 (18.8 mg/l) 5 0/300 19 1/300 Basefuel,
detergent, MDA + AO12 (12 mg/l) 12 0/300 66 13/300 Basefuel,
detergent, MDA + AO13 (10 mg/l) 9 0/300 16 13/300 Basefuel,
detergent, MDA + AO14 (12 mg/l) 52 0/300 17 2/300 Basefuel,
detergent, MDA + AO15 (12 mg/l) 68 0/300 22 0/300 Basefuel,
detergent, MDA + AO16 (9 mg/l) 11 0/300 22 3/300 Basefuel,
detergent, MDA + AO17 (10 mg/l*) 42 0/300 -- -- Basefuel,
detergent, MDA + AO18 (13.8 mg/l) 48 0/300 -- -- *nominally 10 mg/l
however solubility in fuel not good Detergent-2300 ButA Mannich,
active concentration of 100 mg/l. MDA-metal deactivator, active
concentration of 2 mg/l. Concentrations of anti-oxidant linked,
where possible, to the number of moles AO1 in 25 mg. Otherwise 50
mg/l used as standard.
[0211] In at least one the fuels and in some instances in both
fuels, the addition of a phosphorus containing antioxidant to a
package already containing detergent and MDA decreases the amount
of carbon depositing on the surface of the HLPS tube and/or
decreases filter blockage. The traditional antioxidant (BHT--AO1)
tested does not show this effect.
Example 2
[0212] Assessment of Different Detergents in combination with
Preferred Antioxidant
[0213] The preferred anti-oxidant of Example 1, namely AO8, was
combined with three different detergents. The results were compared
against the fuel, MDA, detergent and anti-oxidant alone or in
various combinations. The HLPS data are given below.
3 Shell HT Carbon Composition .mu.gcm.sup.-2 .DELTA.P Basefuel 39
300/230 Basefuel + detergent A 38 0/300 Basefuel + A08 alone (10
86.5 3/300 mg/l) Basefuel + MDA 62 0/300 Basefuel, detergent A + 25
0/300 AO8 Basefuel, detergent A + 39 0/300 MDA Basefuel, detergent
A, 13 0/300 MDA + AO8 Basefuel, detergent B, 23 0/300 MDA + AO8
Basefuel, detergent C, 12 0/300 MDA + AO8 Detergent A-2300 ButA
Mannich, active concentration of 100 mg/l Detergent B-1000/ButA
PIBamine, active concentration of 100 mg/l Detergent C-1000/ButA
PIBSI, active concentration of 100 mg/l MDA-metal deactivator,
active concentration of 2 mg/l.
[0214] Each of the full packages gives better performance than each
component individually at the treat rate used in the package.
Example 3
[0215] Assessment of Package in Different Fuels
[0216] HLPS results for package based on AO8 in different fuels.
For comparison the HPLS results for basefuel and SpecAid 8Q462 at a
treat rate 256 mg/l are also given.
4 .DELTA.P Carbon Carbon Carbon .DELTA.P Spec- .DELTA.P Base
SpecAid Package Fuel Base Aid Package .mu.gcm.sup.-2 .mu.gcm.sup.-2
.mu.gcm.sup.-2 Shell HT 300/230 0/300 0/300 39 10 13 POSF 3684
300/45 0/300 2/300 125 19 17 USAF B Phillips 1/300 0/300 0/300 31
25 3 HT Sunoco 0/300 0/300 0/300 51 35 10.6 Shell 300/170 3/300
0.8/300 157 46 24 Merox USAF A 300/148 0/300 0/300 95 31 9 BP Air
3/300 0/300 0/300 44 33 13 Merox Marathon 4/300 1/300 0/300 55 9 15
HT Phillips 300/27 1/300 0/300 26 46 20 Merox Package contains
AO8-active concentration of 10 mg/l. Detergent-2300 ButA Mannich,
active concentration of 100 mg/l. MDA-metal deactivator, active
concentration of 2 mg/l.
[0217] In all the fuels tested there is a large decrease in both
bulk and surface carbon deposits when using the above additive
package.
[0218] All publications mentioned in the above specification are
herein incorporated 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
* * * * *