U.S. patent application number 13/786674 was filed with the patent office on 2013-09-19 for cold flow improvement of distillate fuels using alpha-olefin compositions.
This patent application is currently assigned to Baker Hughes Incorporated. The applicant listed for this patent is Paul J. Biggerstaff, Ben Morgan, Kimchi T. Phan, John A. Schield, Jack Bradford Ward. Invention is credited to Paul J. Biggerstaff, Ben Morgan, Kimchi T. Phan, John A. Schield, Jack Bradford Ward.
Application Number | 20130239465 13/786674 |
Document ID | / |
Family ID | 49156349 |
Filed Date | 2013-09-19 |
United States Patent
Application |
20130239465 |
Kind Code |
A1 |
Morgan; Ben ; et
al. |
September 19, 2013 |
Cold Flow Improvement of Distillate Fuels Using Alpha-Olefin
Compositions
Abstract
The cold flow of middle distillate fuels may be improved by
adding an effective improving amount of one or more alpha-olefin
compositions. The compositions include, but are not necessarily
limited to, polymers of alpha-olefins per se, copolymerized or
grafted alpha-olefins with maleic anhydride, acrylic acid, vinyl
acetate, alkyl acrylates, methacrylic acid, and/or alkyl
methacrylates. These resulting copolymers or grafted polymers may
be blended with alkylphenol-formaldehyde resins, which in turn may
be blended with ethylene-vinyl acetate (EVA) copolymer. In a
non-limiting example, the cold filter plugging point (CFPP) may be
synergistically improved as compared with the expected additive
effect of using the components separately.
Inventors: |
Morgan; Ben; (Sugar Land,
TX) ; Schield; John A.; (Missouri City, TX) ;
Biggerstaff; Paul J.; (Sugar Land, TX) ; Phan; Kimchi
T.; (Katy, TX) ; Ward; Jack Bradford; (Tulsa,
OK) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Morgan; Ben
Schield; John A.
Biggerstaff; Paul J.
Phan; Kimchi T.
Ward; Jack Bradford |
Sugar Land
Missouri City
Sugar Land
Katy
Tulsa |
TX
TX
TX
TX
OK |
US
US
US
US
US |
|
|
Assignee: |
Baker Hughes Incorporated
Houston
TX
|
Family ID: |
49156349 |
Appl. No.: |
13/786674 |
Filed: |
March 6, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61611864 |
Mar 16, 2012 |
|
|
|
Current U.S.
Class: |
44/351 ; 44/393;
585/10 |
Current CPC
Class: |
C10L 1/1641 20130101;
C10L 1/196 20130101; C10L 10/14 20130101; C10L 1/1905 20130101;
C10L 1/192 20130101; C10L 1/1963 20130101; C10L 1/1955 20130101;
C10L 1/1966 20130101 |
Class at
Publication: |
44/351 ; 44/393;
585/10 |
International
Class: |
C10L 10/14 20060101
C10L010/14; C10L 1/19 20060101 C10L001/19 |
Claims
1. A method for improving cold flow of a distillate fuel comprising
adding to the distillate fuel an effective amount of an additive to
improve a cold flow property, where the additive is selected from
the group consisting of: polymerized alpha-olefins; alpha-olefins
copolymerized or reacted with a second component selected from the
group consisting of maleic anhydride, acrylic acid, vinyl acetate,
alkyl acrylates, methacrylic acid, alkyl methacrylates, and
combinations thereof to give a reaction product; alpha-olefins
copolymerized or reacted with a second component selected from the
group consisting of maleic anhydride, acrylic acid, vinyl acetate,
alkyl acrylates, methacrylic acid, alkyl methacrylates, and
combinations thereof to give a reaction product, where the reaction
product is in turn blended with alkylphenol-formaldehyde resins;
and alpha-olefins copolymerized or reacted with a second component
selected from the group consisting of maleic anhydride, acrylic
acid, vinyl acetate, alkyl acrylates, methacrylic acid, alkyl
methacrylates, and combinations thereof to give a reaction product,
where the reaction product is in turn blended with
alkylphenol-formaldehyde resins, which compositions are further
blended with ethylene-vinyl acetate (EVA) copolymer.
2. The method of claim 1 where the alpha-olefin has from 6 to 30
carbon atoms.
3. The method of claim 1 when: where the alpha-olefin is
copolymerized with or reacted with maleic anhydride, the mole ratio
of maleic anhydride to alpha olefin ranges from about 0.03/1 to
3/1; where the alpha-olefin is copolymerized with or reacted with
acrylic acid, the mole ratio of acrylic acid to alpha-olefin ranges
from about 0.04/1 to about 0.9/1; and where the alpha-olefin is
copolymerized with or reacted with vinyl acetate, the mole ratio of
vinyl acetate to alpha-olefin ranges from about 0.04/1 to about
2/1.
4. The method of claim 1 where: the weight average molecular weight
of the reaction product ranges from about 1000 to about 20,000; the
weight average molecular weight of the alkylphenol-formaldehyde
resins ranges from about 2000 to about 20,000; and the weight
average molecular weight of the EVA copolymer ranges from about
1000 to about 10,000.
5. The method of claim 1 where the effective amount of the additive
ranges from about 10 ppm-vol to about 10,000 ppm-vol.
6. The method of claim 1 where the improved cold flow property is
improved cold filter plugging point (CFPP), and where the CFPP is
improved as compared to an otherwise identical distillate fuel
absent the alpha-olefin component.
7. The method of claim 1 where the additive is not esterified.
8. A method for improving cold flow of a distillate fuel comprising
adding to the distillate fuel from about 10 ppm-vol to about 10,000
ppm-vol of an additive to improve a cold flow property, where the
additive is selected from the group consisting of: polymerized
alpha-olefins; alpha-olefins copolymerized or reacted with a second
component selected from the group consisting of maleic anhydride,
acrylic acid, vinyl acetate, alkyl acrylates, methacrylic acid,
alkyl methacrylates, and combinations thereof to give a reaction
product; alpha-olefins copolymerized or reacted with a second
component selected from the group consisting of maleic anhydride,
acrylic acid, vinyl acetate, alkyl acrylates, methacrylic acid,
alkyl methacrylates, and combinations thereof to give a reaction
product, where the reaction product is in turn blended with
alkylphenol-formaldehyde resins; and alpha-olefins copolymerized or
reacted with a second component selected from the group consisting
of maleic anhydride, acrylic acid, vinyl acetate, alkyl acrylates,
methacrylic acid, alkyl methacrylates, and combinations thereof to
give a reaction product, where the reaction product is in turn
blended with alkylphenol-formaldehyde resins, which compositions
are further blended with ethylene-vinyl acetate (EVA) copolymer;
where the alpha-olefin has from 6 to 30 carbon atoms.
9. The method of claim 8 when: where the alpha-olefin is
copolymerized with or reacted with maleic anhydride, the mole ratio
of maleic anhydride to alpha olefin ranges from about 0.03/1 to
3/1; where the alpha-olefin is copolymerized with or reacted with
acrylic acid, the mole ratio of acrylic acid to alpha-olefin ranges
from about 0.04/1 to about 0.9/1; and where the alpha-olefin is
copolymerized with or reacted with vinyl acetate, the mole ratio of
vinyl acetate to alpha-olefin ranges from about 0.04/1 to about
2/1.
10. The method of claim 8 where: the weight average molecular
weight of the reaction product ranges from about 1000 to about
20,000; the weight average molecular weight of the
alkylphenol-formaldehyde resins ranges from about 2000 to about
20,000; and the weight average molecular weight of the EVA
copolymer ranges from about 1000 to about 10,000.
11. The method of claim 8 where the improved cold flow property is
improved cold filter plugging point (CFPP), and where the CFPP is
improved as compared to an otherwise identical distillate fuel
absent the alpha-olefin component.
12. The method of claim 9 where the additive is not esterified.
13. A distillate fuel composition having improved cold flow
comprising: a distillate fuel; and an effective amount to improve a
cold flow property the distillate fuel of an additive, where the
additive is selected from the group consisting of: polymerized
alpha-olefins; alpha-olefins copolymerized or reacted with a second
component selected from the group consisting of maleic anhydride,
acrylic acid, vinyl acetate, alkyl acrylates, methacrylic acid,
alkyl methacrylates, and combinations thereof to give a reaction
product; alpha-olefins copolymerized or reacted with a second
component selected from the group consisting of maleic anhydride,
acrylic acid, vinyl acetate, alkyl acrylates, methacrylic acid,
alkyl methacrylates, and combinations thereof to give a reaction
product, where the reaction product is in turn blended with
alkylphenol-formaldehyde resins; and alpha-olefins copolymerized or
reacted with a second component selected from the group consisting
of maleic anhydride, acrylic acid, vinyl acetate, alkyl acrylates,
methacrylic acid, alkyl methacrylates, and combinations thereof to
give a reaction product, where the reaction product is in turn
blended with alkylphenol-formaldehyde resins, which compositions
are blended with ethylene-vinyl acetate (EVA) copolymer.
14. The distillate fuel of claim 13 where the alpha-olefin has from
6 to 30 carbon atoms.
15. The distillate fuel of claim 13 when: where the alpha-olefin is
copolymerized with or reacted with maleic anhydride, the mole ratio
of maleic anhydride to alpha olefin ranges from about 0.03/1 to
3/1; where the alpha-olefin is copolymerized with or reacted with
acrylic acid, the mole ratio of acrylic acid to alpha-olefin ranges
from about 0.04/1 to about 0.9/1; and where the alpha-olefin is
copolymerized with or reacted with vinyl acetate, the mole ratio of
vinyl acetate to alpha-olefin ranges from about 0.04/1 to about
2/1.
16. The distillate fuel of claim 13 where: the weight average
molecular weight of the reaction product ranges from about 1000 to
about 20,000; the weight average molecular weight of the
alkylphenol-formaldehyde resins ranges from about 2000 to about
20,000; and the weight average molecular weight of the EVA
copolymer ranges from about 1000 to about 10,000.
17. The distillate fuel of claim 13 where the effective amount of
the additive ranges from about 10 ppm-vol to about 10,000
ppm-vol.
18. The distillate fuel of claim 13 where the improved cold flow
property is improved cold filter plugging point (CFPP), and where
the CFPP is improved as compared to an otherwise identical
distillate fuel absent the alpha-olefin component.
19. The distillate fuel of claim 13 where the additive is not
esterified.
Description
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional
Patent Application 61/611,864 filed Mar. 16, 2012, incorporated
herein by reference in its entirety.
TECHNICAL FIELD
[0002] The present invention relates to improving the cold flow of
distillate fuels, and more particularly relates in one non-limiting
embodiment to improving the cold filter plugging point of middle
distillate fuels by chemical treatment.
TECHNICAL BACKGROUND
[0003] Upon encountering low temperatures, distillate fuels, and in
particular middle distillate fuels, tend to develop fluidity
problems. In one non-limiting definition, middle distillate fuels
include jet fuel, kerosene, heating oil and diesel fuel. More
particularly, the fluidity problems involve paraffins in the fuel
agglomerate at low temperatures to form a waxy semi-solid or
gel-like material that plugs pipes and filters, inhibiting
transmission of the fuel to, for example, an engine.
[0004] Conventionally, this problem is treated by adding to the
fuel a chemical composition called a low temperature fluidity
modifier. The low temperature fluidity modifier can co-crystallize
with or adsorb the paraffins in the fuel oil to precipitate the
paraffin before agglomeration occurs or alternatively to modify
paraffin crystal growth so that the resulting irregularity in size
and shape of the crystals inhibits agglomeration or efficient
packing of the crystals, thereby reducing the tendency toward plug
formation. By contrast, pour point depressants are directed simply
to viscosity reduction of fluids at low temperatures. Pour point
reduction still involves some crystal modification but may not need
to be as efficient or keep the crystals as small. Thus, while
studies have shown a relation between low temperature fluidity of a
fuel and the pour point or cloud point of the fuel, the mechanism
of low temperature fluidity modifier operation and the problem to
which low temperature fluidity modifiers are directed differ
significantly from those of pour point depressants. Therefore,
despite the apparent relationship between low temperature fluidity
and pour point, they typically require different treatments.
Further, it may not be correctly assumed that a low temperature
fluidity modifier will depress the pour point, or that a pour point
depressant will improve low temperature fluidity.
[0005] Because low temperature modifiers operate by affecting the
crystal growth of the paraffins in the fuel being treated, the
selection and composition of a low temperature fluidity modifier
for a particular fuel is based on the nature of the paraffins in
that fuel. For example, low temperature modifiers typically are
coordinated with the paraffins in the fuel so that the solubility
characteristics of the modifier added to the fuel match the
solubility characteristics of the paraffins in the fuel. Thus, if a
fuel contains C.sub.20-24 paraffins that crystallize at 10.degree.
F. (-12.degree. C.), the modifier is typically designed to
crystallize at about 10.degree. F. (-12.degree. C.) as well,
thereby to interfere with the crystallization of the paraffins.
Accordingly, it is well known to those of ordinary skill in the art
of low temperature fluidity modification to select and to adjust
the array of aliphatic chain lengths to balance overall solubility
based on the paraffin content of the fuel to cause the additive to
precipitate out of the fuel at the desired temperature. In fact, it
is common to produce esterified olefin/maleic anhydride copolymers
for use in low temperature fluidity modifier additive compositions
by esterifying certain olefin/maleic anhydride copolymers with an
array of aliphatic alcohols having chain lengths in the range of
from about four to about forty carbon atoms, and to select the
distribution of aliphatic chain lengths in that range in
coordination with the paraffins in the fuel as discussed above.
[0006] U.S. Pat. No. 5,857,287 discloses adding to a fuel oil a
composition of from about 1 to about 40 parts by weight
ethylene/vinyl acetate copolymer having a vinyl acetate content of
from about 10% by weight to about 50% by weight and a weight
average molecular weight of from about 2,000 to about 10,000, and 1
part by weight esterified copolymer of at least one generally
linear alpha-olefin of from about 18 to about 50 carbon atoms and
maleic anhydride in an alpha-olefin to maleic anhydride molar ratio
of from about 4:1 to about 1:2, the copolymer having a weight
average molecular weight of from about 2,000 to about 20,000, the
esterified copolymer having been esterified with a plurality of
aliphatic alcohols having from about four to about forty carbon
atoms, imparts to the fuel oil surprisingly improved low
temperature fluidity, provided that the alcohols include an eight
carbon alcohol making up from about 50 to about 85 molar percent of
the alcohols.
[0007] Despite the existence of a variety of low temperature
fluidity modifiers, none provides completely satisfactory
performance in all fuels. In fact, because of the disparities in
the characteristics of fuel oils, particular low temperature
fluidity modifiers meet with varying success from fuel to fuel.
Thus, there is a continual search for ever more effective low
temperature fluidity modifiers, particularly for use in a variety
of fuels.
SUMMARY
[0008] There is provided, in one non-limiting form, a method for
improving cold flow of a distillate fuel that involves adding to
the distillate fuel an effective amount of an additive to improve a
cold flow property. The additive may include, but is not
necessarily limited to (a) polymerized alpha-olefins per se, (b)
alphaolefins copolymerized or reacted with a second component
selected from the group consisting of maleic anhydride, acrylic
acid, vinyl acetate, alkyl acrylates, methacrylic acid, alkyl
methacrylates, and combinations thereof to give a reaction product,
(c) alpha-olefins copolymerized or reacted with a second component
selected from the group consisting of maleic anhydride, acrylic
acid, vinyl acetate, alkyl acrylates, methacrylic acid, alkyl
methacrylates, and combinations thereof to give a reaction product,
where the reaction product is in turn blended with
alkylphenol-formaldehyde resins, and/or (d) alpha-olefins
copolymerized or reacted with a second component selected from the
group consisting of maleic anhydride, acrylic acid, vinyl acetate,
alkyl acrylates, methacrylic acid, alkyl methacrylates, and
combinations thereof to give a reaction product, where the reaction
product is in turn blended with alkylphenol-formaldehyde resins,
which compositions are further blended with ethylene-vinyl acetate
copolymers (EVA). The alpha-olefin may be understood as a first
component.
[0009] There is also provided in an alternative non-restrictive
embodiment, a distillate fuel composition that includes a
distillate fuel and an additive, where the additive may be selected
from (a), (b), (c) and/or (d) noted above, in an amount effective
to improve the cold flow of the distillate fuel, particularly the
cold filter plugging point (CFPP) of a middle distillate fuel.
[0010] In one non-limiting embodiment the components (a), (b), (c)
and/or (d) are not esterified. In another non-limiting embodiment,
the components (a), (b), (c) and/or (d) do not include esterified
copolymers of alpha-olefins and maleic anhydride.
DETAILED DESCRIPTION
[0011] It has been discovered that compositions which include
polymerized alpha-olefins used alone or alpha-olefins copolymerized
with, grafted with, otherwise reacted with or even simply blended
with additional components will give a synergistic improvement in a
cold flow property of a distillate fuel as compared the expected
sum of the additive effect of the components when used separately.
In particular, unexpected improvement is seen when the improved
cold flow property is compared with an otherwise identical
distillate fuel composition absent the alpha-olefin component.
[0012] One cold flow property that may be improved by the additives
and methods described herein is the cold filter plugging point
(CFPP) which may be defined as the lowest temperature, expressed in
.degree. C. or .degree. F., at which a given volume of a diesel
type of fuel still passes through a standardized filtration device
in a specified time when cooled under certain conditions. This test
gives an estimate for the lowest temperature that a fuel will give
trouble free flow in certain fuel systems. This is important since
in cold temperate countries and environments a high CFPP fuel will
clog up fuel filters and/or fuel lines in vehicle engines more
easily.
[0013] The alpha-olefin suitable for use in the various
compositions herein include those having carbon numbers ranging
from 6 independently to 30, and even higher, in a non-limiting
embodiment. In an alternative, non-restrictive embodiment, the
alpha-olefins may have a carbon number ranging from 10
independently to 28; alternatively from 12 independently to 16.
When "independently" is used in conjunction with a range herein,
any lower threshold may be combined with any upper threshold to
give a suitable alternative range.
[0014] With respect to homopolymers of alpha-olefins, these may
have a weight average molecular weight of from about 1000
independently to about 20,000; alternatively from about 2000
independently to about 10,000.
[0015] Another suitable composition herein includes functionalized
alphaolefins (a first component) copolymerized with or otherwise
reacted with (for instance grafted with) a second component
including, but not necessarily limited to, maleic anhydride,
acrylic acid, vinyl acetate, alkyl acrylates, methacrylic acid,
alkyl methacrylates, and combinations thereof. As used herein, the
"alkyl" in alkyl acrylates and alkyl methacrylates is defined as a
straight or branched alkyl group having carbon numbers ranging from
1 to 8, alternatively from 1 to 4.
[0016] It will be appreciated that it is not always possible to
know when the alpha-olefin is reacted with a second component
whether the reaction is copolymerization, a grafting reaction or
another type of reaction, hence, the interaction is described
herein as "copolymerized or reacted with" to cover all
possibilities by definition. The result is termed a reaction
product. However the reactions are reproducible and the cold flow
property improvement is reproducible for a variety of the polymers,
copolymers and other reaction products.
[0017] Alpha-olefins copolymerized/grafted with maleic anhydride
may have a weight ratio ranging from 1% maleic anhydride to 50%
maleic anhydride of the alpha-olefin, alternatively from 5 wt % to
25 wt % of alpha-olefin. Expressed as mole ratio, the mole ratio of
maleic anhydride to alpha-olefin may range from 0.03/1
independently to 3/1; alternatively from 0.15/1 independently to
2/1.
[0018] Alpha-olefins copolymerized/grafted with acrylic acid may
have a weight ratio ranging from 1% acrylic acid to 20% acrylic
acid to the alpha-olefin, alternatively from 3 wt % to 10 wt % of
alpha-olefin. Expressed as mole ratio, the mole ratio of acrylic
acid to alpha-olefin may range from 0.04/1 independently to 0.9/1;
alternatively from 0.1/1 independently to 0.4/1.
[0019] Alpha-olefins copolymerized/grafted with vinyl acetate may
have a weight ratio ranging from 1% vinyl acetate to 40% vinyl
acetate of the alphaolefin, alternatively from 10 wt % to 25 wt %
of alpha-olefin. Expressed as mole ratio, the mole ratio of vinyl
acetate to alpha-olefin may range from 0.04/1 independently to 2/1;
alternatively from 0.4/1 independently to 1/1.
[0020] With respect to copolymers, graft polymers or other reaction
products with the alpha-olefins, these reaction products may have a
weight average molecular weight of from about 1000 independently to
about 20,000; alternatively from about 2000 independently to about
10,000. For the alkylphenol-formaldehyde resin components, they may
range in weight average molecular weight from about 2000
independently to about 20,000; alternatively from about 5000
independently to about 12,000. For the EVA copolymer components,
they may range in weight average molecular weight from about 1000
independently to about 10,000; alternatively from about 2000
independently to about 4000.
[0021] The alpha-olefins may be homopolymerized using methods well
known in the art, and further, the alpha-olefins may be reacted
with the second components using methods well known in the art.
These polymerization and other reactions may be carried out at a
temperature between about 60 and about 180.degree. C., and a
pressure between about 0 and about 200 psig. The reactions may be
carried out in the absence or presence of a catalyst. If a catalyst
is used, suitable catalysts include, but are not necessarily
limited to, peroxide catalysts, such as di-t-butyl peroxide,
benzoyl peroxide, lauroyl peroxide, and t-butyl hydroperoxide and
the like.
[0022] As noted previously, the functionalized alpha-olefins (that
is, those reacted with a second component selected from the group
consisting of maleic anhydride, acrylic acid, vinyl acetate, alkyl
acrylates, methacrylic acid, alkyl methacrylates, and combinations
thereof) may be blended with alkylphenol-formaldehyde resins. In
one non-limiting embodiment the weight ratio of the functionalized
alpha-olefins with alkylphenol-formaldehyde resins ranges from
about 5/1 independently to about 100/1; alternatively from about
1/1 independently to about 20/1.
[0023] Further, the functionalized alpha-olefins noted above may be
blended with alkylphenol-formaldehyde resins, and further blended
with ethylene-vinyl acetate copolymers (EVA). In these blends or
further reactions, the amount of EVA may range from about 99%
independently to about 1 wt %; alternatively from about 98%
independently to about 2 wt %, based on the amount of
functionalized alpha-olefins and alkylphenol-formaldehyde
resin.
[0024] With respect to determining the effective amount of the
additive useful to obtain the best results in the distillate fuel,
e.g. middle distillate fuel, one good suitable procedure is simply
empirical testing, since as previously noted, the cold flow
improver may need to be matched to the paraffins in the fuel.
Nevertheless, to give some idea of suitable dosage ranges for these
cold flow improvers, if the alpha-olefin portion that is blended or
reacted with the second component or EVA ranges between about 1
independently to about 50 vol %, alternatively between about 5
independently to about 20 vol %, then the dosage range in middle
distillate fuels of the final product blend or reaction product
would be about 10 ppm-vol independently to about 10,000 ppm-vol;
alternatively from about 50 ppm-vol independently to about 500
ppm-vol. In other words, the dosage of the alpha-olefin portion
would range between about 1 ppm-vol independently to about 5,000
ppm-vol; alternatively from about 2.5 ppm-vol independently to
about 100 ppm-vol.
[0025] The middle distillate fuels in which the methods and
compositions described herein are expected to be effective include,
but are not necessarily limited to, jet fuel, kerosene, heating oil
and diesel fuel, whether or not they include fatty acid methyl
esters (FAME). The now common practice of introducing FAME into
middle distillate fuels may lead to additional wax crystal
formation from saturated FAME. Additionally, some fuel companies
are considering adding hydrogenated vegetable oils as biofuel
components, which may introduce further paraffinic waxes into the
middle distillate fuels. However, the additives and methods
described herein are expected to be effective in these fuels as
well. The distillate fuels as described herein do not encompass
polymerized alpha-olefins (PAO) as a major component thereof, that
is, a synthetic fuel where PAO is a major (more than 50 volume
percent) component thereof. In other words, PAO is not a synthetic
base stock for the fuels herein.
[0026] It is expected that the additives described herein will be
compatible with other conventional fuel additives.
[0027] The invention will now be described with reference to
particular Examples which are not intended to limit the invention
but rather simply to illuminate it further.
Examples 1-9
[0028] CFPP tests were run for three four different middle
distillate fuels: Kern, Coffeyville, Cenex #3, and Hovensa. The
components are as defined in Table I.
TABLE-US-00001 TABLE I Cold Flow Improver Additives DF5063 EVA
polymer, 50% active* T3005 EVA polymer, 50% active C1608 C30+
alpha-olefin-maleic anhydride polymer, 25% active 1787-123 C20-24
alpha-olefin-acrylic acid polymer, 50% active 1787-125 C20-24
alpha-olefin-acrylic acid polymer, 80% active 1787-189
C20-24/C24-28 alpha-olefin polymer, 25% active 1789-001 C20-24
alpha-olefin-vinyl acetate, (polymer) 25% active 1789-097 C20-24 +
C24-28 alpha-olefin-vinyl acetate (19%), (polymer) 25% active
1789-155 C20-24 + C24-28 alpha-olefin-vinyl acetate (9.5%),
(polymer) 25% active *Active refers to actual polymer; the balance
is aromatic solvent.
[0029] Table II presents the CFPP test results for four different
fuels using a total of 200 ppm (includes solvent) dosage for each
Example, except the blank. The comparative Examples are 2 and 4
where no alpha-olefin component is present. It may be seen that the
other Examples, which had an alpha-olefin component, gave
noticeable and unexpected improvements as compared to Examples 2
and 4. More specifically, compare Examples 3 and 6-9 with Example
2, and compare Example 5 with Example 4.
TABLE-US-00002 TABLE II CFPP Test Results ppm Ex. Additive dose
Kern Coffeyville Cenex#3 Hovensa 1 Blank 0 -4 F. (-20 C.) 9 F. (-13
C.) 9 F. (-13 C.) 18 F. (-8 C.) 2 DF5063 200 0 F. (-18 C.) -15 F.
(-26 C.) 5 F. (-15 C.) 16 F. (-9 C.) 3 DF5063/ 180/20 -26 F. (-32
C.) -17 F. (-27 C.) -- -- C1608 4 T3005 200 -8 F. (-22 C.) -18 F.
(-28 C.) -- -- 5 T3005/ 180/20 -29 F. (-34 C.) -18 F. (-28 C.) --
-- C1608 6 DF5063/ 200/20 -- -- -8 F. (-22 C.) -- 1787-123 7
DF5063/ 200/20 -- -- -11 F. (-24 C.) -- 1787-125 8 DF5063/ 180/20
-26 F. (-32 C.) -16 F. (-27 C.) -17 F. (-27 C.) -- 1787-189 9
DF5063/ 180/20 -22 F. (-30 C.) -16 F. (-27 C.) -16 F. (-27 C.) --
1789-001 10 DF5063/ 180/40 -29 F. (-34 C.) -- -15 F. (-26 C.) -6 F.
(-21 C.) 1787-189 11 DF5063/ 180/20 -31 F. (-35 C.) -- -15 F. (-26
C.) -2 F. (-19 C.) 1789-097 12 DF5063/ 180/20 -26 F. (-32 C.) -- -9
F. (-23 C.) -4 F. (-20 C.) 1789-155
[0030] It is to be understood that the invention is not limited to
the exact details of reactants, proportions and dosages mentioned
and described, as modifications and equivalents thereof will be
apparent to one skilled in the art. The invention is therefore to
be limited only by the scope of the appended claims. Further, the
specification is to be regarded in an illustrative rather than a
restrictive sense. For example, specific combinations of
alpha-olefin components and second components, full esters of
alpha-olefin-maleic anhydride copolymers, half esters of
alpha-olefin-maleic anhydride copolymers, different
alkylphenol-formaldehyde resins, different proportions of the
various reactants and the like falling within the described
parameters herein, but not specifically identified or tried in a
particular composition method or apparatus, are expected to be
within the scope of this invention.
[0031] The terms "comprises" and "comprising" used in the claims
herein should be interpreted to mean including, but not limited to,
the recited elements.
[0032] The present invention may also suitably comprise, consist of
or consist essentially of the elements disclosed and may be
practiced in the absence of an element not disclosed. For instance,
the method for improving cold flow of a distillate fuel may consist
of or consist essentially of adding to the distillate fuel an
effective amount of an additive to improve a cold flow property,
where the additive is (a) polymerized alpha-olefins, (b)
alpha-olefins copolymerized or reacted with a second component
selected from the group consisting of maleic anhydride, acrylic
acid, vinyl acetate, alkyl acrylates, methacrylic acid, alkyl
methacrylates, and combinations thereof to give a reaction product,
(c) alpha-olefins copolymerized or reacted with a second component
selected from the group consisting of maleic anhydride, acrylic
acid, vinyl acetate, alkyl acrylates and combinations thereof to
give a reaction product, where the reaction product is in turn
blended with alkylphenol-formaldehyde resins, and/or (d)
alphaolefins copolymerized or reacted with a second component
selected from the group consisting of maleic anhydride, acrylic
acid, vinyl acetate, alkyl acrylates and combinations thereof to
give a reaction product, where the reaction product is in turn
blended with alkylphenol-formaldehyde resins, which compositions
are further blended EVA copolymers.
[0033] Alternatively there may be provided a distillate fuel
composition having improved cold flow that consists of or consists
essentially of a distillate fuel and an effective amount to improve
a cold flow property of the distillate fuel of an additive, where
the additive is either (a), (b), (c) and/or (d) as described
above.
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