U.S. patent application number 16/565772 was filed with the patent office on 2020-03-26 for compositions containing diesel and fatty acid methyl ester/maleic anhydride/esters (fame/ma/esters) and the use of fame/ma/ester.
The applicant listed for this patent is The United States of America, as Represented by the Secretary of Agriculture. Invention is credited to Gerhard H. Knothe, Jing Li, Zengshe Liu.
Application Number | 20200095514 16/565772 |
Document ID | / |
Family ID | 69883092 |
Filed Date | 2020-03-26 |
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United States Patent
Application |
20200095514 |
Kind Code |
A1 |
Liu; Zengshe ; et
al. |
March 26, 2020 |
Compositions Containing Diesel and Fatty Acid Methyl Ester/Maleic
Anhydride/Esters (FAME/MA/Esters) and the Use of FAME/MA/Esters to
Improve the Lubricity of Diesel
Abstract
A composition containing diesel (e.g., containing less than
about 15 ppm sulfur) and fatty acid methyl ester/maleic
anhydride/esters (FAME/MA/esters), wherein the FAME/MA/esters are
prepared by a method involving reacting FAME with MA to form
FAME/MA and reacting FAME/MA with alkyl alcohol to form
FAME/MA/esters; wherein the FAME is conjugated. The FAME/MA/esters
are produced from tung oil or from plant oils in which the
unsaturated fatty acids have been converted to conjugated fatty
acids. Also a method of improving the lubricity of diesel,
involving combining diesel and FAME/MA/esters, wherein the
FAME/MA/esters are prepared by a method involving reacting FAME
with MA to form FAME/MA and reacting FAME/MA with alkyl alcohol to
form FAME/MA/esters; wherein the FAME is conjugated.
Inventors: |
Liu; Zengshe; (Morton,
IL) ; Knothe; Gerhard H.; (Peoria, IL) ; Li;
Jing; (Nanjing, CN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The United States of America, as Represented by the Secretary of
Agriculture |
Washington |
DC |
US |
|
|
Family ID: |
69883092 |
Appl. No.: |
16/565772 |
Filed: |
September 10, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62733774 |
Sep 20, 2018 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10L 2200/0476 20130101;
C10L 2200/0263 20130101; C10L 2270/026 20130101; C10L 2200/0446
20130101; C10L 10/08 20130101; C10L 1/1905 20130101; C10L 1/1915
20130101 |
International
Class: |
C10L 1/19 20060101
C10L001/19; C10L 10/08 20060101 C10L010/08 |
Claims
1. A composition comprising diesel and FAME/MA/esters, wherein said
FAME/MA/esters are prepared by a method comprising reacting FAME
with MA to form FAME/MA and reacting FAME/MA with alkyl alcohol to
form FAME/MA/esters; wherein said FAME is conjugated.
2. The composition according to claim 1, wherein said diesel
contains less than about 15 ppm sulfur.
3. The composition according to claim 1, wherein said
FAME/MA/esters are produced from tung oil.
4. The composition according to claim 1, wherein said
FAME/MA/esters are produced from plant oils in which the
unsaturated fatty acids have been converted to conjugated fatty
acids.
5. A method of improving the lubricity of diesel, said method
comprising combining diesel and FAME/MA/esters, wherein said
FAME/MA/esters are prepared by a method comprising reacting FAME
with MA to form FAME/MA and reacting FAME/MA with alkyl alcohol to
form FAME/MA/esters; wherein said FAME is conjugated.
6. The method according to claim 5, wherein said diesel contains
less than about 15 ppm sulfur.
Description
REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional
Application No. 62/733,774, filed 20 Sep. 2018, which is
incorporated herein by reference in its entirety.
BACKGROUND OF THE INVENTION
[0002] Disclosed herein are compositions containing diesel (e.g.,
containing less than about 15 ppm sulfur) and fatty acid methyl
ester/maleic anhydride/esters (FAME/MA/esters), wherein the
FAME/MA/esters are prepared by a method involving reacting FAME
with MA to form FAME/MA and reacting FAME/MA with alkyl alcohol to
form FAME/MA/esters; wherein the FAME is conjugated. The
FAME/MA/esters are produced from tung oil or from plant oils in
which the unsaturated fatty acids have been converted to conjugated
fatty acids. Also disclosed are methods of improving the lubricity
of diesel, involving combining diesel and FAME/MA/esters, wherein
the FAME/MA/esters are prepared by a method involving reacting FAME
with MA to form FAME/MA and reacting FAME/MA with alkyl alcohol to
form FAME/MA/esters; wherein the FAME is conjugated.
[0003] Recently, the use of ultralow-sulfur diesel (ULSD) fuels
containing less than about 15 ppm sulfur, as required by
regulations in the United States, Europe, and elsewhere, has led to
the failure of diesel engine parts such as fuel injectors and pumps
because they are lubricated by the fuel itself (Knothe, G., and K.
R. Steidley, Energy & Fuels, 19: 1192-1200 (2005); Lacey, P.
I., and S. R. Westbrook, Lubricity Requirement of Low Sulfur Diesel
Fuels, SAE Tech. Pap. Ser., 950248 (1995); Wei, D., and H. A.
Spikes, Wear, 111: 217-235 (1986); Lacey, P. I., and S. J. Lestz,
Effect of Low-Lubricity Fuels on Diesel Injection Pumps--Part I:
Field Performance, SAE Tech. Pap. Ser., 920823 (1992); Lacey, P.
I., and S. J. Lestz, Effect of Low-Lubricity Fuels on Diesel
Injection Pumps--Part II: Laboratory Evaluation, SAE Tech. Pap.
Ser., 920824 (1992); Nikanjam, M., and P. T. Henderson, Lubricity
of Low Sulfur Diesel Fuels, SAE Tech. Pap. Ser., 932740 (1993);
Wang, J. C., and D. J. Reynolds, The Lubricity Requirement of Low
Sulfur Diesel Fuels, SAE Tech. Pap. Ser., 942015 (1994); Tucker, R.
F., et al., The Lubricity of Deeply Hydrogenated Diesel Fuels--The
Swedish Experience, SAE Tech. Pap. Ser., 942016 (1994); Wall, S.
W., et al., Pet. Coal, 41: 38-42 (1999); Dimitrakis, W. J.,
Hydrocarbon Eng., 8: 37-39 (2003)). The poor lubricity of ULSD
requires additives or blending with another fuel of sufficient
lubricity to regain lubricity (Knothe and Steidley, 2005; Lacey and
Westbrook, 1995; Wei and Spikes, 1986; Lacey and Lestz, 1992; Lacey
and Lestz, 1992; Nikanjam and Henderson, 1993; Wang and Reynolds,
1994; Tucker et al., 1994; Wall et al., 1999; Dimitrakis, 2003).
Blending with another fuel necessitates a higher percentage of
another fuel of sufficient lubricity to regain lubricity and
increases the cost with higher concentration up to about 10-20%
(Lacey, P. I., et al., Effects of High Temperature and Pressure on
Fuel Lubricated Wear, SAE Tech. Pap. Ser. 2001, 2001-01-3523;
Hughes, J. M., et al., Ind. Eng. Chem., 41: 1386-1388 (2002)). For
example, improvement of lubricity by blending with biodiesel
typically requires at least 1% (10,000 ppm), even better 2% (20,000
ppm), of such fuel (Knothe and Steidley, 2005). Therefore,
economically it is better to enhance the lubricity of ULSD by
adding additives at additive levels (e.g., <1% instead of
.gtoreq.1% blend). There is currently a need for better additives
for ULSD fuels.
[0004] Herein we describe the synthesis of tung oil based fatty
acid methyl ester (FAME) which we call EAME. EAME (or other FAME)
can be reacted with maleic anhydride through Diels-Alder reaction
to form maleation products, named EAME/MA (or other FAME/MA. The
EAME/MA (or other FAME/MA) can then be esterified with short chain
alcohols to produce a product which can be used, for example, as a
diesel additive. Also described are the lubricity data for neat
petrodiesel and petrodiesel that contains the esterification
products of EAME/MA as additives were evaluated by using the
high-frequency reciprocating rig (HFRR) (ASTM D-6079, ISO 12156)
lubricity tester.
SUMMARY OF THE INVENTION
[0005] Disclosed herein are compositions containing diesel (e.g.,
containing less than about 15 ppm sulfur) and fatty acid methyl
ester/maleic anhydride/esters (FAME/MA/esters), wherein the
FAME/MA/esters are prepared by a method involving reacting FAME
with MA to form FAME/MA and reacting FAME/MA with alkyl alcohol to
form FAME/MA/esters; wherein the FAME is conjugated. The
FAME/MA/esters are produced from tung oil or from plant oils in
which the unsaturated fatty acids have been converted to conjugated
fatty acids. Also disclosed are methods of improving the lubricity
of diesel, involving combining diesel and FAME/MA/esters, wherein
the FAME/MA/esters are prepared by a method involving reacting FAME
with MA to form FAME/MA and reacting FAME/MA with alkyl alcohol to
form FAME/MA/esters; wherein the FAME is conjugated.
[0006] This summary is provided to introduce a selection of
concepts in a simplified form that are further described below in
the detailed description. This summary is not intended to identify
key features or essential features of the claimed subject matter,
nor is it intended as an aid in determining the scope of the
claimed subject matter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] The patent or application file contains at least one drawing
executed in color. Copies of this patent or patent application
publication with color drawing(s) will be provided by the Office
upon request and payment of the necessary fee.
[0008] Exemplary FIG. 1 shows the FT-IR spectra of tung oil raw
material and chemically modified compounds as described below.
[0009] Exemplary FIG. 2 shows the .sup.1H-NMR of chemically
modified compounds as described below.
[0010] Exemplary FIG. 3 shows the .sup.13C-NMR of chemically
modified compounds as described below.
DETAILED DESCRIPTION OF THE INVENTION
[0011] Disclosed herein are compositions containing diesel (e.g.,
containing less than about 15 ppm sulfur) and fatty acid methyl
ester/maleic anhydride/esters (FAME/MA/esters), wherein the
FAME/MA/esters are prepared by a method involving reacting FAME
with MA to form FAME/MA and reacting FAME/MA with alkyl alcohol to
form FAME/MA/esters; wherein the FAME is conjugated. The
FAME/MA/esters are produced from tung oil or from plant oils in
which the unsaturated fatty acids have been converted to conjugated
fatty acids. Also disclosed are methods of improving the lubricity
of diesel, involving combining diesel and FAME/MA/esters, wherein
the FAME/MA/esters are prepared by a method involving reacting FAME
with MA to form FAME/MA and reacting FAME/MA with alkyl alcohol to
form FAME/MA/esters; wherein the FAME is conjugated.
[0012] We have produced tung oil-based fatty acid methyl ester
(FAME) which we call EAME because of its high content (e.g.,
greater than 80%) of eleostearic acid in the tung oil. EAME can be
reacted with maleic anhydride through Diels-Alder reaction to form
maleation products, named EAME/MA. The EAME/MA can then be
esterified with short chain alcohols (e.g., C1-4 alcohols such as
methanol, ethanol, butanol, etc.) to produce a diesel additive. An
example of the maleation of FAME (e.g., EAME) and esterification of
FAME (e.g., EAME) maleation compound is shown in the Scheme
below:
##STR00001##
[0013] The FAME must have conjugated double bonds (i.e., at least
two C.dbd.C and one single bond between the C.dbd.C;
--C.dbd.C--C.dbd.C--) and tung oil is naturally conjugated. Other
conjugated FAMEs can be prepared according to methods reported by
Larock et al. (Larock, R. C. et al., J. Am. Oil Chem. Soc., 2001,
78: 447-453 (2001)); such conjugated FAMEs include, for example,
conjugated vegetable oils, conjugated linoleic acid, and conjugated
ethyl linoleate.
[0014] These esterified compounds were added into ULSD with
concentrations ranging from 100 ppm and 500 ppm and 1000 ppm. Their
lubricity was tested by using a high-frequency reciprocating rig
(HFRR) lubricity tester (ASTM D-6079, ISO 12156). Lubricity
determined per the HFRR test can be evaluated using the lubricity
specification for petrodiesel fuel in the petrodiesel standards EN
590 and ASTM D975. The maximum wear scars called for in these
petrodiesel standards are 460 .mu.m and 520 .mu.m, respectively.
The results show that wear scar diameters of ULSD fuel additized
with, for example, EAME/MA esters are reduced by 7%, 40% and 48%
with EAME/MA ester concentrations from 100 ppm to 1000 ppm, and
frictions are reduced by 6%, 30% and 47%, respectively, compared to
the neat ULSD.
[0015] Other compounds (e.g., known ULSD additives (e.g., oxidants)
known in the art) may be added to the composition provided they do
not substantially interfere with the intended activity and efficacy
of the composition; whether or not a compound interferes with
activity and/or efficacy can be determined, for example, by the
procedures utilized below. For example, the phrase "optionally
comprising a known ULSD additive" means that the composition may or
may not contain a known ULSD additives and that this description
includes compositions that contain and do not contain a known ULSD
additive. Also, by example, the phrase "optionally adding a known
ULSD additive" means that the method may or may not involve adding
a known ULSD additive and that this description includes methods
that involve and do not involve adding a ULSD additive.
[0016] "Optional" or "optionally" means that the subsequently
described event or circumstance may or may not occur, and that the
description includes instances in which said event or circumstance
occurs and instances where it does not. For example, the phrase
"optionally comprising a defoaming agent" means that the
composition may or may not contain a defoaming agent and that this
description includes compositions that contain and do not contain a
defoaming agent. Also, by example, the phrase "optionally adding a
defoaming agent" means that the method may or may not involve
adding a defoaming agent and that this description includes methods
that involve and do not involve adding a defoaming agent.
[0017] By the term "effective amount" of a compound or property as
provided herein is meant such amount as is capable of performing
the function of the compound or property for which an effective
amount is expressed. As will be pointed out below, the exact amount
required will vary from process to process, depending on recognized
variables such as the compounds employed and the processing
conditions observed. Thus, it is not possible to specify an exact
"effective amount." However, an appropriate effective amount may be
determined by one of ordinary skill in the art using only routine
experimentation.
[0018] While this invention may be embodied in many different
forms, there are described in detail herein specific preferred
embodiments of the invention. The present disclosure is an
exemplification of the principles of the invention and is not
intended to limit the invention to the particular embodiments
illustrated. All patents, patent applications, scientific papers,
and any other referenced materials mentioned herein are
incorporated by reference in their entirety. Furthermore, the
invention encompasses any possible combination of some or all of
the various embodiments and characteristics described herein and/or
incorporated herein. In addition the invention encompasses any
possible combination that also specifically excludes any one or
some of the various embodiments and characteristics described
herein and/or incorporated herein.
[0019] The amounts, percentages and ranges disclosed herein are not
meant to be limiting, and increments between the recited amounts,
percentages and ranges are specifically envisioned as part of the
invention. All ranges and parameters disclosed herein are
understood to encompass any and all subranges subsumed therein, and
every number between the endpoints. For example, a stated range of
"1 to 10" should be considered to include any and all subranges
between (and inclusive of) the minimum value of 1 and the maximum
value of 10 including all integer values and decimal values; that
is, all subranges beginning with a minimum value of 1 or more,
(e.g., 1 to 6.1), and ending with a maximum value of 10 or less,
(e.g. 2.3 to 9.4, 3 to 8, 4 to 7), and finally to each number 1, 2,
3, 4, 5, 6, 7, 8, 9, and 10 contained within the range.
[0020] Unless otherwise indicated, all numbers expressing
quantities of ingredients, properties such as molecular weight,
reaction conditions (e.g., reaction time, temperature), percentages
and so forth as used in the specification and claims are to be
understood as being modified in all instances by the term "about."
Accordingly, unless otherwise indicated, the numerical properties
set forth in the following specification and claims are
approximations that may vary depending on the desired properties
sought to be obtained in embodiments of the present invention. As
used herein, the term "about" refers to a quantity, level, value,
or amount that varies by as much as 10% to a reference quantity,
level, value, or amount.
[0021] Unless defined otherwise, all technical and scientific terms
used herein have the same meaning as commonly understood by one of
ordinary skill in the art to which the invention belongs. Although
any methods and materials similar or equivalent to those described
herein can be used in the practice or testing of the present
invention, the preferred methods and materials are now
described.
[0022] The following examples are intended only to further
illustrate the invention and are not intended to limit the scope of
the invention as defined by the claims.
Examples
[0023] Materials: Tung oil was purchased from Alnor Oil Company,
Inc. (Valley Stream, N.Y.). It had a yellow color and a specific
gravity of 0.935-0.940 at 25.degree. C. Maleic anhydride (MA) and
p-toluenesulfonic acid (PTS) were obtained from Sigma-Aldrich (St.
Louis, Mo.). Tung oil fatty acid esters (EAME) were prepared using
a transesterification process reported to convert a vegetable oil
into biodiesel (Knothe, G., and R. O. Dunn, Biofuels Derived from
Vegetable Oils and Fats, IN Oleochemical Manufacture and
Applications; Gunstone, F. D., and R. J. Hamilton, Eds; Sheffield
Academic Press: Sheffield, U. K., 2001, pp 106-163.)
[0024] Preparation of FAME from Tung oil: In a 3 neck round bottom
flask fitted with reflux condenser, thermometer and addition port,
50 g of tung oil and 12 ml methanol were added and stirred at
60.degree. C. and 2.78 ml sodium methoxide (25 weight % in
methanol) was added and allowed to react for 1 hour. Then the
temperature was allowed to fall to room temperature and 50 ml
hexane was added. In a separatory funnel the reaction mixture was
allowed to separate with the upper layer containing the methyl
esters and the lower glycerol layer was removed. The methyl esters
were washed with DI water three times until pH neutral, dried over
magnesium sulfate, and then filtered. A rotary evaporator was used
to remove the hexane and any remaining methanol. The product was
named as EAME. Alternatively, C2-C4 alcohols can be used instead of
methanol.
[0025] Preparation of EAME/MA and Esterification with Methanol and
Butanol: First, EAME (9.0 g, 30.8 mmol) and MA (3.17 g, 32.4 mmol)
were placed in a 250 mL round-bottom flask equipped with a silicone
oil bath and a magnetic stirrer. Nitrogen was bubbled through the
mixture for 5 min at room temperature, followed by stirring at
150.degree. C. for 2 h in N.sub.2 atmosphere to give a clear, dark
yellow and viscous liquid, termed EAME/MA. In the second step, PTS
(180 mg, 2 wt % to EAME/MA) and methanol (10.0 mL, 247.4 mmol,
i.e., molar ratio methanol to EAME/MA 8:1) were inserted into the
reactor. The reaction mixture was stirred and heated at 65.degree.
C. to reflux for 3 h. Then, excess methanol and by-produced water
were removed by vacuum-rotary evaporation. 10.0 mL of fresh
methanol was added and the same operation repeated twice.
Eventually the final product methylated EAME/MA (EAME/MA ester) was
obtained through subsequent neutralization, water wash,
separations, and vacuum drying. The products were named as
EAME/MA/ME. Alternatively, C2-C4 alcohols can be used instead of
methanol. In addition, other conjugated FAMEs can be used instead
of EAME.
[0026] The high-frequency reciprocating rig (HFRR) (ASTM D-6079,
ISO 12156) lubricity tester has been used for lubricity tests
because the HFRR method is more user-friendly and is also suitable
for pressurization to study the lubricity of fuels (Lacey, P. I.,
et al., Lubricity of Volatile Fuels for Compression Ignition
Engines, SAE Tech. Pap. Ser., 2000-01-1804 (2000)). The HFRR method
has also been described as being more severe than pump tests
(Crockett, R. M., et al., Tribol. Lett., 16: 187-194 (2004)). The
prescribed maximum wear scars are 460 .mu.m (60.degree. C.) in the
European petrodiesel standard EN 590, and 520 .mu.m (60.degree. C.)
in the American petrodiesel standard, ASTM D-975. These standards
are used to indicate fuels with sufficient lubricity for practical
use in a diesel engine, whereas fuels generating wear scars above
those limits may or may not be acceptable.
[0027] Lubricity Determination: Lubricity determinations were
performed at 60.degree. C. (controlled to less than 1.degree. C.)
according to the standard method ASTM D-6079 with an HFRR lubricity
tester obtained from PCS Instruments (London, England) via Lazar
Scientific (Granger, Ind.). Controlling the humidity to 30%-50% was
necessary for the HFRR test to give reproducible results, which was
accomplished according to the standard with a potassium carbonate
bath (50% humidity). In addition to the usual wear scar data of the
HFRR ball, we determined the friction data (coefficient of
friction) and film data (electrical resistance) recorded by the
software during the experiments.
[0028] Characterization: Chemically modified tung oil fatty acid
methyl ester (EAME), maleation product (EAMA/MA) and esterification
products (EAME/MAME and EAMA/MA/BU) were characterized by FT-IR,
.sup.1H-NMR, and .sup.13C-NMR; spectra are shown in FIG. 1, FIG. 2,
and FIG. 3, respectively.
[0029] In the FTIR spectrum of EAME/MA, the strong peak observed at
1055 cm-1 in FIG. 1 was assigned to the double bond C--H bending of
MA. The strong band at 993 cm-1 was attributed to the conjugated
double bonds of tung oil and EAME, but this band became a weak
absorption peak at EAME/MA and EAME/MA/esters due to the maleation
reaction (Liu, C. G., et al., Industrial Crops and Products, 71:
185-196 (2015)). The typical anhydride C.dbd.O stretching of MA
were found at 1849 and 1776 cm-1 for EAME/MA, but these two peaks
almost disappeared after esterification, the ester C.dbd.O
stretching peak at 1720 cm-1 became strong as seen in the
bio-lubricant spectra.
[0030] All starting materials and final products were also examined
by .sup.1H NMR and .sup.13C NMR (see FIG. 2 and FIG. 3). It was
noted that no peak existed at 7.1 ppm in the .sup.1H NMR spectrum
of the EAMA/MA in FIG. 2, which indicated no unreacted MA was left
after purification. New bands appeared around 3.5 ppm which
represented the protons at the structures where MA attached onto
EAMA. The bands at 5.3-6.4 ppm, which corresponded to the protons
on the conjugated triene structures of EAME, decreased
significantly due to the maleation reaction between MA and the
C.dbd.C bonds on the EAME chain. In the .sup.13C NMR spectrum (FIG.
3), new bands signals appeared at 44-48 ppm, which represented the
connecting structure between MA and the EAME chain. The peaks at
126-136 ppm denoting the C.dbd.C bonds on EAME chains also
decreased significantly. Finally, two peaks at around 172-174 ppm,
which denoted the carbonyl carbons on the attached anhydride
groups, appeared at EAME/MA and disappeared at EAMA/MA esters
because of esterification. Surprisingly, all these results
indicated that MA grafted onto EAME effectively and esterification
products were confirmed.
[0031] Lubricity: Lubricity was assessed using the ASTM D-6079
(HFRR) method at 60.degree. C. Table 1 gives the wear scar values
of ULSD and ULSD with additives. Lubricity as determined per the
HFRR test can be evaluated using the lubricity specification in the
petrodiesel standard ASTM D975. The low-lubricity ULSD exhibited
very poor lubricity in the neat form (Table 1) with a wear scar
value of 550 .mu.m. The neat samples of EAME-MA-ME or EAME-MA-BU in
Table 1 surprisingly showed excellent lubricity, as demonstrated by
the low wear scar values, about 100 .mu.m and 200 .mu.m,
respectively. These results prompted us to prepare samples in
which, initially, 100 ppm, 500 ppm and 1000 ppm of EAME-MA-ME or
EAME-MA-BU were added to the low-lubricity petrodiesel fuels
(ULSD). The effect of the lubricity additive in ULSD was clearly
visible. It can be seen that both samples surprisingly performed
excellently. Adding the samples at 500 ppm appeared to induce
sufficient lubricity to low-lubricity ULSD fuel. The additives
reduced the wear scar of ULSD by 40%. There appeared to be little
to no advantage applying a 1000 ppm level. On the other hand, for
friction data, the 1000 ppm level performed a little better than
the 500 ppm level, as it was reduced by 46% and 47%,
respectively.
[0032] Lubricity of two additives, polyalphaolefin PAO-6[cSt] and
Kendex.RTM. 0150H, have been tested with high-frequency
reciprocating rig (HFRR) with EAME compounds. Polyalphaolefin PAO-6
(Durasyn 166) was received from Ineos Oligomers (League City, Tex.)
with specifications: specific gravity, 0.828 g/mL (ASTM D 4052);
kinematic viscosity at 40 and 100.degree. C., 31.13 and 5.91 cSt,
respectively (ASTM D 445); pour point, -66.degree. C. (ASTM D 97).
Hydrotreated heavy paraffinic mineral oil (Kendex.RTM. 0150H), a
Group I base oil, was obtained from American Refining Group
(Bradford, Pa.) and had the specifications: specific gravity, 0.864
g/mL (ASTM D 4052); kinematic viscosity at 40 and 100.degree. C.,
27 and 5.2 cSt, respectively (ASTM D 445); pour point,
<-9.degree. C. (ASTM D 97); sulfur content, <300 ppm (ASTM D
5183, four ball test).
[0033] HFRR results are shown in Table 2. It was noticed that with
1000 ppm of EAME-MA-BU, the wear scars surprisingly were reduced
24.5% and 25.6% for 150H GP1 Base Oil and 166 POA, respectively.
However, the EAME-MA-ME surprisingly reduced 11.0% and 29.0% for
150H GP1 Base Oil and 166 POA, respectively. The EAME-MA-ME
responded better for 166 POA than for 150H GP1 Base Oil.
[0034] FAMEs prepared from Linseed oil and Black Currant reacted
with maleic acid by ene-reaction, and then carried out ring opening
by methanol and butanol. The formed compounds were tested with
high-frequency reciprocating rig (HFRR) for ultralow-sulfur diesel
(ULSD) fuels. The results showed that lubricity of ULSD with 500
ppm and 1000 ppm concentrations of the formed compounds through
ene-reaction surprisingly was not improved. The reason was that
fatty acids from Linseed oil and Black Currant are not conjugated
fatty acids; thus they reacted with maleic anhydride through
ene-reaction, not through Diels-Alder addition. That is why
concentration of modified vegetable oils in patent EP 1 093 509 B1
showed that it needs more than 1%, or 2% (10,000 ppm and 20,000
ppm) to blend with biodiesels to improve their lubricity.
[0035] Conclusions: Surprisingly, the present results obtained with
the high-frequency reciprocating rig (HFRR) lubricity tester gave
clear data that short chain esters of EAME-MA compound effectively
enhanced the lubricity of ULSD. The lubricity of ULSD at low
additive levels (about 500 ppm to about 1000 ppm) surprisingly was
greatly improved. The additive concentrations were 200 and 400
times lower than blending biodiesel at 1%-2%.
[0036] All of the references cited herein, including U.S. Patents
and U.S. Patent Application Publications, are incorporated by
reference in their entirety.
[0037] Thus, in view of the above, there is described (in part) the
following:
[0038] A composition comprising (or consisting essentially of or
consisting of) diesel and FAME/MA/esters, wherein said
FAME/MA/esters are prepared by a method comprising (or consisting
essentially of or consisting of) reacting FAME with MA to form
FAME/MA and reacting FAME/MA with alkyl alcohol to form
FAME/MA/esters; wherein said FAME is conjugated. The above
composition, wherein said diesel contains less than about 15 ppm
sulfur. The above composition, wherein said FAME/MA/esters are
produced from tung oil. The above composition, wherein said
FAME/MA/esters are produced from plant oils in which the
unsaturated fatty acids have been converted to conjugated fatty
acids.
[0039] A method of improving the lubricity of diesel, said method
comprising (or consisting essentially of or consisting of)
combining diesel and FAME/MA/esters, wherein said FAME/MA/esters
are prepared by a method comprising (or consisting essentially of
or consisting of) reacting FAME with MA to form FAME/MA and
reacting FAME/MA with alkyl alcohol to form FAME/MA/esters; wherein
said FAME is conjugated. The above method, wherein said diesel
contains less than about 15 ppm sulfur.
[0040] The term "consisting essentially of" excludes additional
method (or process) steps or composition components that
substantially interfere with the intended activity of the method
(or process) or composition, and can be readily determined by those
skilled in the art (for example, from a consideration of this
specification or practice of the invention disclosed herein).
[0041] The invention illustratively disclosed herein suitably may
be practiced in the absence of any element (e.g., method (or
process) steps or composition components) which is not specifically
disclosed herein. Thus the specification includes disclosure by
silence ("Negative Limitations In Patent Claims," AIPLA Quarterly
Journal, Tom Brody, 41(1): 46-47 (2013): " . . . Written support
for a negative limitation may also be argued through the absence of
the excluded element in the specification, known as disclosure by
silence . . . . Silence in the specification may be used to
establish written description support for a negative limitation. As
an example, in Ex parte Lin [No. 2009-0486, at 2, 6 (B.P.A.I. May
7, 2009)] the negative limitation was added by amendment . . . . In
other words, the inventor argued an example that passively complied
with the requirements of the negative limitation . . . was
sufficient to provide support . . . . This case shows that written
description support for a negative limitation can be found by one
or more disclosures of an embodiment that obeys what is required by
the negative limitation . . . ."
[0042] Other embodiments of the invention will be apparent to those
skilled in the art from a consideration of this specification or
practice of the invention disclosed herein. It is intended that the
specification and examples be considered as exemplary only, with
the true scope and spirit of the invention being indicated by the
following claims.
TABLE-US-00001 TABLE 1 High-Frequency Reciprocating Rig (HFRR) Data
of Petrodiesel and with Additives Wear Scars (.mu.m) Results HFRR
(60.degree. C.) Ball Ball Red. Disc Disc Film Red. Sample ID X Y
Avg. % X Y % Friction % ULSD neat 557 542 550 540 1318 9 0.448 559
500 530 585 1272 10 0.408 EAME-MA-ME 100 ppm 515 458 487 535 1264
14 0.373 555 485 520 6.9 564 1295 16 0.353 6.4 EAME-MA-ME 500 ppm
279 277 278 321 1117 83 0.343 390 330 360 40.0 407 1167 68 0.255
30.0 EAME-MA-ME 1000 ppm 371 278 325 400 1110 74 0.233 377 281 329
40.0 389 1125 77 0.232 46.0 EAME-MA-BU 100 ppm 513 451 482 514 1231
12 0.382 559 484 522 7.0 546 1255 12 0.405 8.1 EAME-MA-BU 500 ppm
348 283 316 372 1130 71 0.242 321 257 289 40.0 318 1112 87 0.219
46.0 EAME-MA-BU 1000 ppm 304 227 266 312 1053 89 0.231 337 242 290
48.0 372 1081 86 0.220 47.0 EAME-MA-ME Neat 98 83 91 80 1082 97
0.065 116 99 108 85 968 93 0.066 EAME-MA-BU Neat 252 157 205 296
1022 79 0.135 243 142 193 270 1010 87 0.125
TABLE-US-00002 TABLE 2 Wear Scars (.mu.m) Results HFRR (60.degree.
C.) Ball Ball Red. Disc Disc Film Red. Sample ID X Y Avg. % X Y %
Friction % 150H GP1 Base Oil-neat 304 293 299 275 103 64 0.215 301
284 293 288 1108 63 0.213 150H GP1 Base Oil 313 269 291 296 1096 72
0.211 +100 ppm EAME-MA- 309 272 291 1.7 302 1089 77 0.203 3.3 ME
150H GP1 Base Oil 308 259 284 331 1099 75 0.205 +100 ppm EAME-MA-
298 217 258 8.4 321 1053 82 0.197 6.1 ME 150H GP1 Base Oil 304 255
280 284 1089 81 0.204 +100 ppm EAME-MA- 264 230 247 11.0 266 1095
89 0.194 7.0 ME 150H GP1 Base Oil 301 253 277 276 1094 72 0.212
+100 ppm EAME-MA- 330 286 308 1.2 303 1124 61 0.221 0 BU 150H GP1
Base Oil 316 259 288 319 1135 76 0.205 +500 ppm EAME-MA- 274 256
265 6.6 270 1073 80 0.211 2.8 BU 150H GP1 Base Oil 267 125 196 299
1025 92 0.195 +1000 ppm EAME-MA- 282 220 251 24.5 301 1044 86 0.196
8.6 BU Durasyn 166 POA-neat 320 290 305 281 1099 42 0.256 312 281
297 294 1092 42 0.261 Durasyn 166 POA 313 280 297 262 1108 64 0.217
+100 ppm EAME-MA- 314 288 301 0.7 295 1110 47 0.246 10.6 ME Durasyn
166 POA 319 277 298 303 1095 59 0.224 +500 ppm EAME-MA- 317 297 307
0 303 1098 58 0.226 13.1 ME Durasyn 166 POA 259 131 195 262 1039 91
0.198 +1000 ppm EAME-MA- 257 206 232 29.0 299 1036 90 0.189 25.3 ME
Durasyn 166 POA 305 271 288 269 1093 52 0.231 +100 ppm EAME-MA- 317
263 290 4.0 270 1079 64 0.215 13.9 BU Durasyn 166 POA 339 287 313
328 1130 69 0.216 +500 ppm EAME-MA- 327 263 295 1.0 322 1102 68
0.216 16.6 BU Durasyn 166 POA 261 176 219 254 1025 94 0.193 +1000
ppm EAME-MA- 286 172 229 25.6 285 1027 93 0.194 25.3 BU
* * * * *