U.S. patent application number 12/593383 was filed with the patent office on 2010-05-06 for antioxidant blends for fatty acid methyl esters (biodiesel).
This patent application is currently assigned to Albemarie Corporation. Invention is credited to Vincent J. Gatto, Emily Schneller, Gangkai Zhao.
Application Number | 20100107481 12/593383 |
Document ID | / |
Family ID | 39639792 |
Filed Date | 2010-05-06 |
United States Patent
Application |
20100107481 |
Kind Code |
A1 |
Gatto; Vincent J. ; et
al. |
May 6, 2010 |
ANTIOXIDANT BLENDS FOR FATTY ACID METHYL ESTERS (BIODIESEL)
Abstract
This invention provides stabilized biodiesels comprising (1)
biodiesel, such as fatty acid methyl ester (FAME), (2) mono- or
bis-hindered phenolic derived from 2,6-di-tert-butylphenol, and (3)
N,N'-di-substituted para-phenylene diamine. Also methods of
stabilizing biodiesel are provided involving adding (2) and (3) to
(1).
Inventors: |
Gatto; Vincent J.; (Baton
Rouge, LA) ; Zhao; Gangkai; (Shanghai, CN) ;
Schneller; Emily; (Brandon, FL) |
Correspondence
Address: |
ALBEMARLE CORPORATION;PATENT DEPARTMENT
451 FLORIDA STREET
BATON ROUGE
LA
70801
US
|
Assignee: |
Albemarie Corporation
Baton Rouge
LA
|
Family ID: |
39639792 |
Appl. No.: |
12/593383 |
Filed: |
March 13, 2008 |
PCT Filed: |
March 13, 2008 |
PCT NO: |
PCT/US08/56763 |
371 Date: |
September 28, 2009 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60908551 |
Mar 28, 2007 |
|
|
|
60908546 |
Mar 28, 2007 |
|
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Current U.S.
Class: |
44/388 |
Current CPC
Class: |
C10L 1/2235 20130101;
C10L 1/14 20130101; Y02E 50/13 20130101; C10L 1/19 20130101; Y02P
30/20 20151101; C10L 1/1832 20130101; C10G 2300/1011 20130101; C10L
1/223 20130101; C10L 1/1835 20130101; Y02E 50/10 20130101; C10L
1/183 20130101 |
Class at
Publication: |
44/388 |
International
Class: |
C10L 1/19 20060101
C10L001/19 |
Claims
1. A composition derived from biodiesel, mono- or bis-hindered
phenolic derived from 2,6-di-tert-butylphenol, and
N,N'-di-substituted para-phenylene diamine, wherein the combined
amount of the mono- or bis-hindered phenolic and the
N,N'-di-substituted para-phenylene diamine is from about 50 ppm to
about 5000 ppm based on the biodiesel.
2. The composition of claim 1 wherein (a) the biodiesel consists
essentially of crude biodiesel; (b) the mono- or bis-hindered
phenolic derived from 2,6-di-tert-butylphenol comprises: (i)
ortho-tert-butylphenol, (ii) 2,6-di-tert-butylphenol, (iii)
2,4,6-tri-tert-butylphenol, (iv)
4,4'-methylenebis(2,6-di-tert-butylphenol), (v)
3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamicacid, methyl ester,
(vi) 3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamicacid, C7-C9
branched alkyl esters, (vii)
2,6-di-tert-butyl-alpha-dimethylamino-p-cresol, or (viii) butylated
hydroxytoluene; and (c) the N,N'-di-substituted para-phenylene
diamine comprises: (i) N,N'-di-sec-butyl-p-phenylenediamine, (ii)
N,N'-diisopropyl-p-phenylenediamine, or (iii)
N,N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine.
3. The composition of claim 2 wherein the crude biodiesel is
derived from soybean oil, canola oil, palm oil, coconut oil,
rapeseed oil, corn oil, or used vegetable oil.
4. The composition of claim 2 wherein the crude biodiesel is a
fatty acid methyl ester.
5. The composition of claim 1 wherein (a) the biodiesel consists
essentially of distilled biodiesel; (b) the mono- or bis-hindered
phenolic derived from 2,6-di-tert-butylphenol comprises: (i)
ortho-tert-butylphenol, (ii) 2,6-di-tert-butylphenol, (iii)
2,4,6-tri-tert-butylphenol, (iv)
4,4'-methylenebis(2,6-di-tert-butylphenol), (v)
3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamicacid, methyl ester,
(vi) 3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamicacid, C7-C9
branched alkyl esters, (vii)
2,6-di-tert-butyl-alpha-dimethylamino-p-cresol, or (viii) butylated
hydroxytoluene; and (c) the N,N'-di-substituted para-phenylene
diamine comprises: (i) N,N'-di-sec-butyl-p-phenylenediamine, (ii)
N,N'-diisopropyl-p-phenylenediamine, or (iii)
N,N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine.
6. The composition of claim 5 wherein the distilled biodiesel is
derived from soybean oil, canola oil, palm oil, coconut oil,
rapeseed oil, corn oil, or used vegetable oil.
7. The composition of claim 1 wherein the combined amount of the
mono- or bis-hindered phenolic and the N,N'-di-substituted
para-phenylene diamine is from about 100 ppm to 2500 ppm based on
the biodiesel.
8. The composition according to claim 1 wherein the weight ratio of
the 2,4,6-tri-tert-butylphenol to the N,N'-di-substituted
para-phenylene diamine is: a) greater than about 1; b) greater than
about 1.25; or c) greater than about 1.5.
9. A composition derived from biodiesel,
2,4,6-tri-tert-butylphenol, and N,N'-di-substituted para-phenylene
diamine, wherein the weight ratio of the 2,4,6-tri-tert-butylphenol
to the N,N'-di-substituted para-phenylene diamine is a) greater
than about 1.
10. The composition according to claim 9 wherein the ratio of the
2,4,6-tri-tert-butylphenol to the N,N'-di-substituted
para-phenylene diamine is from about 10:1 to about 1:10 by on
weight.
11. A composition prepared by combining biodiesel, mono- or
bis-hindered phenolic derived from 2,6-di-tert-butylphenol, and
N,N'-di-substituted para-phenylene diamine, wherein the combined
amount of the mono- or bis-hindered phenolic and the
N,N'-di-substituted para-phenylene diamine is from about 50 ppm to
about 5000 ppm based on the biodiesel.
12. The composition of claim 11 wherein (a) the biodiesel consists
essentially of crude biodiesel; (b) the mono- or bis-hindered
phenolic derived from 2,6-di-tert-butylphenol comprises: (i)
ortho-tert-butylphenol, (ii) 2,6-di-tert-butylphenol, (iii)
2,4,6-tri-tert-butylphenol, (iv)
4,4'-methylenebis(2,6-di-tert-butylphenol), (v)
3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamicacid, methyl ester,
(vi) 3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamicacid, C7-C9
branched alkyl esters, (vii)
2,6-di-tert-butyl-alpha-dimethylamino-p-cresol, or (viii) butylated
hydroxytoluene; and (c) the N,N'-di-substituted para-phenylene
diamine comprises: (i) N,N'-di-sec-butyl-p-phenylenediamine, (ii)
N,N'-diisopropyl-p-phenylenediamine, or (iii)
N,N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine.
13. The composition of claim 11 wherein (a) the biodiesel consists
essentially of distilled biodiesel; (b) the mono- or bis-hindered
phenolic derived from 2,6-di-tert-butylphenol comprises: (i)
ortho-tert-butylphenol, (ii) 2,6-di-tert-butylphenol, (iii)
2,4,6-tri-tert-butylphenol, (iv)
4,4'-methylenebis(2,6-di-tert-butylphenol), (v)
3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamicacid, methyl ester,
(vi) 3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamicacid, C7-C9
branched alkyl esters, (vii)
2,6-di-tert-butyl-alpha-dimethylamino-p-cresol, or (viii) butylated
hydroxytoluene; and (c) the N,N'-di-substituted para-phenylene
diamine comprises: (i) N,N'-di-sec-butyl-p-phenylenediamine, (ii)
N,N'-diisopropyl-p-phenylenediamine, or (iii)
N,N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine.
14. A composition comprising biodiesel, 2,4,6-tri-tert-butylphenol,
and N,N'-di-substituted para-phenylene diamine, wherein the weight
ratio of the 2,4,6-tri-tert-butylphenol to the N,N'-di-substituted
para-phenylene diamine is a) greater than about 1.
15. The composition according to claim 14 wherein the ratio of the
2,4,6-tri-tert-butylphenol to the N,N'-di-substituted
para-phenylene diamine is from about 10:1 to about 1:10 by on
weight.
16. A method of improving oxidation stability of a composition
comprising biodiesel by combining the composition and mono- or
bis-hindered phenolic derived from 2,6-di-tert-butylphenol, and
N,N'-di-substituted para-phenylene diamine such that the combined
amount of the mono- or bis-hindered phenolic and the
N,N'-di-substituted para-phenylene diamine is from about 50 ppm to
5000 ppm based on the biodiesel.
17. The method of claim 16 wherein (a) the biodiesel consists
essentially of crude biodiesel; (b) the mono- or bis-hindered
phenolic derived from 2,6-di-tert-butylphenol comprises: (i)
ortho-tert-butylphenol, (ii) 2,6-di-tert-butylphenol, (iii)
2,4,6-tri-tert-butylphenol, (iv)
4,4'-methylenebis(2,6-di-tert-butylphenol), (v)
3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamicacid, methyl ester,
(vi) 3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamicacid, C7-C9
branched alkyl esters, (vii)
2,6-di-tert-butyl-alpha-dimethylamino-p-cresol, or (viii) butylated
hydroxytoluene; and (c) the N,N'-di-substituted para-phenylene
diamine comprises: (i) N,N'-di-sec-butyl-p-phenylenediamine, (ii)
N,N'-diisopropyl-p-phenylenediamine, or (iii)
N,N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine.
18. The method of claim 17 wherein the crude biodiesel is derived
from soybean oil, canola oil, palm oil, coconut oil, rapeseed oil,
corn oil, or used vegetable oil.
19. The method of claim 17 wherein the crude biodiesel is a fatty
acid methyl ester.
20. The method of claim 16 wherein (a) the biodiesel consists
essentially of distilled biodiesel; (b) the mono- or bis-hindered
phenolic derived from 2,6-di-tert-butylphenol comprises: (i)
ortho-tert-butylphenol, (ii) 2,6-di-tert-butylphenol, (iii)
2,4,6-tri-tert-butylphenol, (iv)
4,4'-methylenebis(2,6-di-tert-butylphenol), (v)
3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamicacid, methyl ester,
(vi) 3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamicacid, C7-C9
branched alkyl esters, (vii)
2,6-di-tert-butyl-alpha-dimethylamino-p-cresol, or (viii) butylated
hydroxytoluene; and (c) the N,N'-di-substituted para-phenylene
diamine comprises: (i) N,N'-di-sec-butyl-p-phenylenediamine, (ii)
N,N'-diisopropyl-p-phenylenediamine, or (iii)
N,N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine.
21. The method of claim 120 wherein the distilled biodiesel is
derived from soybean oil, canola oil, palm oil, coconut oil,
rapeseed oil, corn oil, or used vegetable oil.
22. The method of claim 16 wherein the combined amount of the mono-
or bis-hindered phenolic and the N,N'-di-substituted para-phenylene
diamine is from about 100 ppm to 2500 ppm based on the
biodiesel.
23. The method according to claim 16 wherein the weight ratio of
the 2,4,6-tri-tert-butylphenol to the N,N'-di-substituted
para-phenylene diamine is a) greater than about 1.
24. The method according to claim 16 wherein the ratio of the
2,4,6-tri-tert-butylphenol to the N,N'-di-substituted
para-phenylene diamine is from about 10:1 to about 1:10 by on
weight.
Description
BACKGROUND
[0001] As worldwide energy demand continues to increase and
reserves of fossil fuels shrink, the diversification of energy
sources becomes increasingly important. Biodiesel is one way to
achieve diversification. Biodiesel is a generic name for mono-alkyl
esters of long-chain fatty acids derived from renewable lipid
sources such as vegetable oils, animal fats, or used cooking oils
and fats. Biodiesel fuels have many names, depending on the
feedstocks used to produce them, for example, fatty acid methyl
ester (FAME), rapeseed methyl ester (RME), used vegetable oil
methyl ester (UVOME), soybean oil methyl ester (SOME) or palm oil
methyl ester (POME). Biodiesel feedstocks vary widely in their
fatty acid compositions (chain length and saturation).
[0002] Biodiesel is typically produced by the reaction of a
vegetable oil or an animal fat with an alcohol, such as methanol,
in the presence of a catalyst to yield methyl esters (the
biodiesel) and glycerine. The most commonly used catalyst,
potassium hydroxide, is used in transesterification of a wide range
of oils and fats, from vegetable to animal, from virgin to used,
including those with the highest acid contents. The thus produced
biodiesel can be distilled to remove excess alcohols and other
impurities. Other methods for production of biodiesel are
known.
[0003] Freshly produced vegetable oils are protected from oxidation
by the presence of naturally occurring antioxidants (for example,
tocopherols). However, the manufacturing process for biodiesel
tends to remove some of the natural antioxidants, leaving the fuel
less protected from oxidative degradation. In addition,
distillation of the biodiesel tends to remove essentially all the
natural antioxidants leaving the fuel even further unprotected from
oxidative degradation. Oxidation of biodiesel by contact with air
and metal surfaces results in the formation of hydroperoxides.
These induce free-radical chain reactions that lead to
decomposition into low-molecular-weight, highly oxidized species
(aldehydes, ketones, acids) and high-molecular-weight polymeric
materials (gums). These gums tend to cause poor combustion and
other engine problems such as deposits on injectors and pistons.
The presence of high-molecular weight, insoluble gums generally
leads to fuel-filter plugging.
[0004] The RANCIMAT test is a widely accepted method for measuring
the oxidation stability of biodiesel. This test consists of
bubbling air through biodiesel that has been heated to 110.degree.
C. The amount of short-chain acids present in the distillate (the
cleavage products of the fatty acid oxidation) is a direct
indication of the oxidation stability of the biodiesel. In Europe
and Brazil, biodiesel has to fulfill a six-hour RANCIMAT test
requirement at the production plant and at the pump when refueling
vehicles, irrespective of the age of the biodiesel. Other countries
may institute similar requirements. Although freshly produced
biodiesel may show an oxidation stability (measured by the RANCIMAT
method) of more than six hours, this value will decrease over time
under common storage conditions if no antioxidants are present.
[0005] Antioxidants are used in hydrocarbon fuels to increase
oxidation stability. The oxidation stability of biodiesel can also
be increased by the addition of antioxidants. However, given the
relative youth of biodiesel fuels as compared to hydrocarbon fuels,
antioxidant technology for biodiesel is not as well-developed.
[0006] Thus, there is a need for improved antioxidant compositions
for use in biodiesel fuels and for biodiesel compositions
comprising such antioxidant compositions that are economically
suited for commercial use.
THE INVENTION
[0007] This invention meets the above-described needs by providing
compositions derived from biodiesel, mono- or bis-hindered phenolic
derived from 2,6-di-tert-butylphenol, and N,N'-di-substituted
para-phenylene diamine, wherein the combined amount of the mono- or
bis-hindered phenolic and the N,N'-di-substituted para-phenylene
diamine is from about 50 ppm to about 5000 ppm based on the
biodiesel. Further, such compositions are provided wherein the
biodiesel is crude biodiesel, and wherein the crude biodiesel is
derived from soybean oil, canola oil, palm oil, coconut oil,
rapeseed oil, corn oil, or used vegetable oil, and wherein the
crude biodiesel is a fatty acid methyl ester. Such compositions are
provided wherein the biodiesel is distilled biodiesel, and wherein
the distilled biodiesel is derived from soybean oil, canola oil,
palm oil, coconut oil, rapeseed oil, corn oil, or used vegetable
oil. Also, such compositions are provided wherein the combined
amount of the mono- or bis-hindered phenolic and the
N,N'-di-substituted para-phenylene diamine is from about 100 ppm to
2500 ppm based on the biodiesel. Further, such compositions are
provided wherein the ratio of the mono- or bis-hindered phenolic to
N'N-di-substituted para-phenylene diamine varies from about 10:1 to
about 1:10 by weight, in particular varies from about 5:1 to about
1:5 by weight. Also provided are compositions derived from
biodiesel, 2,4,6-tri-tert-butylphenol, and N,N'-di-substituted
para-phenylene diamine, wherein the ratio of the
2,4,6-tri-tert-butylphenol to the N,N'-di-substituted
para-phenylene diamine varies from about 10:1 to about 1:10 by
weight. This invention also provides compositions prepared by
combining, or comprising, biodiesel, mono- or bis-hindered phenolic
derived from 2,6-di-tert-butylphenol, and N,N'-di-substituted
para-phenylene diamine, wherein the combined amount of the mono- or
bis-hindered phenolic and the N,N'-di-substituted para-phenylene
diamine is from about 50 ppm to about 5000 ppm based on the
biodiesel.
[0008] This invention also provides methods of improving oxidation
stability of a composition comprising biodiesel by combining the
composition and mono- or bis-hindered phenolic derived from
2,6-di-tert-butylphenol, and N,N'-di-substituted para-phenylene
diamine such that the combined amount of the mono- or bis-hindered
phenolic and the N,N'-di-substituted para-phenylene diamine is from
about 50 ppm to 5000 ppm based on the biodiesel. Also provided are
such methods wherein the biodiesel is crude biodiesel, and wherein
the crude biodiesel is derived from soybean oil, canola oil, palm
oil, coconut oil, rapeseed oil, corn oil, or used vegetable oil,
and wherein the crude biodiesel is a fatty acid methyl ester. Also
provided are such methods wherein the biodiesel is distilled
biodiesel, and wherein the distilled biodiesel is derived from
soybean oil, canola oil, palm oil, coconut oil, rapeseed oil, corn
oil, or used vegetable oil. Also, such methods are provided wherein
the combined amount of the mono- or bis-hindered phenolic and the
N,N'-di-substituted para-phenylene diamine is from about 100 ppm to
2500 ppm based on the biodiesel. Further, such methods are provided
wherein the ratio of the mono- or bis-hindered phenolic to
N'N-di-substituted para-phenylene diamine is varies from about 10:1
to about 1:10 by weight, in particular varies from about 5:1 to
about 1:5 by weight. Also provided are methods of improving
oxidation stability of a composition comprising biodiesel by
combining the composition, 2,4,6-tri-tert-butylphenol, and
N,N'-di-substituted para-phenylene diamine, wherein the ratio of
the 2,4,6-tri-tert-butylphenol to the N,N'-di-substituted
para-phenylene diamine varies from about 5:1 to about 1:5 by
weight.
[0009] In this invention, the mono- or bis-hindered phenolic
derived from 2,6-di-tert-butylphenol can comprise
ortho-tert-butylphenol, 2,6-di-tert-butylphenol,
2,4,6-tri-tert-butylphenol,
4,4'-methylenebis(2,6-di-tert-butylphenol),
3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamicacid, methyl ester,
3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamicacid, C7-C9 branched
alkyl esters, 2,6-di-tert-butyl-alpha-dimethylamino-p-cresol;
butylated hydroxytoluene, or 2,4,6-tri-tert-butylphenol; and the
N,N'-di-substituted para-phenylene diamine can comprise
N,N'-di-sec-butyl-p-phenylenediamine,
N,N'-diisopropyl-p-phenylenediamine, or
N,N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine.
[0010] In some of the compositions and/or methods of the present
invention, the weight ratio of the 2,4,6-tri-tert-butylphenol to
the N,N'-di-substituted para-phenylene diamine is greater than
about 1, in some embodiments, greater than about 1.25, and in other
embodiments, greater than about 1.5.
[0011] A glossary of terms is provided prior to the claims.
[0012] We were surprised to discover the substantial increase in
oxidation stability of biodiesel provided by this invention. We did
not have reason to expect that the combinations of biodiesels and
antioxidants as described and claimed herein would provide the
benefits shown by the examples provided herein.
Mono or Bis-Hindered Phenolics Derived from
2,6-Di-Tert-Butylphenol
[0013] Suitable mono or bis-hindered phenolics derived from
2,6-di-tert-butylphenols can comprise 2,6-di-tert-butylphenol
(e.g., the product comprising 2,6-di-tert-butylphenol sold under
the trademark ETHANOX 4701); 2,4,6-tri-tert-butylphenol;
combinations of ortho-tert-butylphenol, 2,6-di-tert-butylphenol,
and 2,4,6-tri-tert-butylphenol (e.g., the product comprising
ortho-tert-butylphenol, 2,6-di-tert-butylphenol, and
2,4,6-tri-tert-butylphenol sold under the trademark ETHANOX 4733);
combinations of 2,6-di-tert-butylphenol and
2,4,6-tri-tert-butylphenol (e.g., the product comprising
2,6-di-tert-butylphenol and 2,4,6-tri-tert-butylphenol sold under
the trademark ETHANOX 4735);
4,4'-methylenebis(2,6-di-tert-butylphenol) (e.g., the product
comprising 4,4'-methylenebis(2,6-di-tert-butylphenol) sold under
the trademark ETHANOX 4702);
3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamicacid, methyl ester
(e.g., the product comprising
3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamicacid, methyl ester
sold under the trademark ETHANOX 4750);
3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamicacid, C7-C9 branched
alkyl esters (e.g., the product comprising
3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamicacid, C7-C9 branched
alkyl esters sold under the trademark ETHANOX 4716);
2,6-di-tert-butyl-alpha-dimethylamino-p-cresol (e.g., the product
comprising 2,6-di-tert-butyl-alpha-dimethylamino-p-cresol sold
under the trademark ETHANOX 4703); butylated hydroxytoluene (BHT);
essentially 100% 2,4,6-tri-tert-butylphenol (TTBP), or combinations
thereof. In this invention, concentration of the mono or
bis-hindered phenolic derived from 2,6-di-tert-butylphenol can be
from about 0.0025 wt % to about 0.25 wt % of the total
biodiesel.
N,N'-Di-Substituted Para-Phenylene Diamines
[0014] Suitable N,N'-di-substituted para-phenylene diamines can
comprise N,N'-di-sec-butyl-p-phenylenediamine (PDA),
N,N'-diisopropyl-p-phenylenediamine,
N,N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine, or combinations
thereof. In this invention, concentration of the
N,N'-dis-substituted para-phenylene diamine can be from about
0.0025 wt % to about 0.25 wt % of the total biodiesel.
Biodiesels
[0015] As used herein, unless otherwise distinguished, the term
biodiesel comprises crude biodiesel, distilled biodiesel, or any
individual chemical component of either. Crude biodiesel comprises
8 carbon to 22 carbon saturated, mono-unsaturated, di-unsaturated,
or tri-unsaturated methyl ester, or fatty acid methyl ester derived
from a vegetable or animal source. Processes for producing crude
biodiesel are well know to those skilled in the art. Example
individual chemical components of fatty acid methyl ester include
methyl stearate (n-octadecanoic acid, methyl ester), methyl oleate
(9-octadecenoic acid, methyl ester), methyl vaccenate
(11-octadecenoic acid methyl ester), methyl linoleate
(9,12-octadecadienoic acid, methyl ester), or methyl linoleniate
(9,12,15-octadecatrienoic acid, methyl ester), caprylic acid methyl
ester, capric acid methyl ester, lauric acid methyl ester, myristic
acid methyl ester, palmitic acid methyl ester, arachidic acid
methyl ester, behenic acid methyl ester, lauroleic acid methyl
ester, myristoleic acid methyl ester, palmitoleic acid methyl
ester, elaidic acid methyl ester, gadoleic acid methyl ester,
arachidonic acid methyl ester, erucic acid methyl ester, and the
like.
[0016] Distilled biodiesel comprises crude biodiesel that has been
subjected to at least one distillation step, e.g., to remove excess
alcohols, residual glycerine, and other impurities, and includes
biodiesel obtained as a specific cut or fraction produced during
the distillation of crude biodiesel. Methods of distilling crude
biodiesel are well known to those skilled in the art.
[0017] Crude biodiesel can be derived from any suitable vegetable
or animal source, including for example soybean oil, low erucic
acid rapeseed oil (Canola Oil), high erucic acid rapeseed oil, palm
oil, used cooking oil, vegetable oil, coconut oil, corn oil,
cottonseed oil, safflower oil, sunflower oil, peanut oil, sugar
cane oil, lard, tallow, poultry fat, yellow grease, and the like.
Fatty acid methyl ester in crude biodiesel can be produced, e.g.,
by a transesterification reaction between a vegetable or animal
based triglyceride and methanol using a catalyst, as is familiar to
those skilled in the art.
[0018] Crude biodiesel or distilled biodiesel can be subjected to
additional chemical treatment, e.g., to reduce unsaturation.
Combinations
[0019] Compositions according to this invention comprising, or
prepared by combining, biodiesel, mono or bis-hindered phenolic
derived from 2,6-di-tert-butylphenol (component (2)), and
N,N'-di-substituted para-phenylene diamine (component (3)), can
comprise, or be prepared by combining, from about 50 ppm to about
5000 ppm of components (2) and (3), based on the amount of the
biodiesel, and can comprise, or be prepared by combining, from
about 100 ppm to about 2500 ppm of components (2) and (3), based on
the amount of the biodiesel.
[0020] Methods of improving oxidation stability of biodiesel
according to this invention can comprise combining the biodiesel
and from about 50 ppm to about 5000 ppm of antioxidant component
comprising mono or bis-hindered phenolic derived from
2,6-di-tert-butylphenol and N,N'-di-substituted para-phenylene
diamine. Such methods can also comprising combining the biodiesel
component and from about 100 ppm to about 2500 ppm of antioxidant
component comprising mono or bis-hindered phenolic derived from
2,6-di-tert-butylphenol and N,N'-di-substituted para-phenylene
diamine.
EXAMPLES
[0021] The following examples are illustrative of the principles of
this invention. It is understood that this invention is not limited
to any one specific embodiment exemplified herein, whether in the
examples or the remainder of this patent application.
[0022] In each example summarized in Table 1, the identified
biodiesel sample and antioxidant composition were combined. In some
of the comparative examples, no antioxidant composition was added
to the identified biodiesel. In the examples in which the biodiesel
was distilled, the biodiesel was distilled using standard
techniques known to those skilled in the art. In each example, the
oxidation stability of the combination (or of just the biodiesel in
certain of the comparative examples) was tested with the RANCIMAT
test using RANCIMAT test method (DIN EN 14112). In each instance
the sample size was 3 grams, the temperature was 110.degree. C.,
the air source was purified dry air, and the flow rate was 10 L/hr.
The data in Table 1 clearly shows the benefits of this invention.
For example, for soybean oil methyl ester, distilled, with no
antioxidant added, the highest RANCIMAT result was 1.7 hour (see
comparative example nos. 33-39); whereas, for soybean oil methyl
ester, distilled, with antioxidant added in accordance with this
invention, the RANCIMAT results ranged from 3.87 hours to 11.19
hours (see example nos. 1-22). For soybean oil methyl ester, not
distilled, with no antioxidant added, the highest RANCIMAT result
was 4.63 hours (see comparative example nos. 40 and 41); whereas,
for soybean oil methyl ester, not distilled, with antioxidant added
in accordance with this invention, the RANCIMAT results ranged from
6.46 hours to 9.28 hours (see example nos. 23-32). Comparing
comparative example nos. 42 and 44, both of which show results of
combining soybean oil methyl ester, distilled and antioxidant
composition of 300 ppm ETHANOX 4733 and 100 ppm of a component not
of this invention, to example nos. 1, 3, 5, and 6 of this
invention, each of which shows results of combining soybean oil
methyl ester, distilled and antioxidant composition of less than
300 ppm ETHANOX 4733 and PDA, shows that each of example nos. 1, 3,
5, and 6 has a better RANCIMAT result (8.76 hrs, 9.53 hrs, 6.91
hrs, and 5.89 hrs, respectively) than either of comparative example
nos. 42 and 44 (2.94 hrs and 2.88 hrs, respectively). Comparing
comparative example nos. 43, 45, and 46, each of which shows
results of combining soybean oil methyl ester, distilled and
antioxidant composition of 300 ppm ETHANOX 4702 and 100 ppm of a
component not of this invention, to example 2 of this invention,
which shows results of combining soybean oil methyl ester,
distilled and antioxidant composition of 200 ppm ETHANOX 4702 and
200 ppm PDA, shows that example no. 2 has a better RANCIMAT result
(10.52 hrs) than any of example nos. 43, 45, and 46 (3.6 hrs, 3.87
hrs, and 4.06 hrs, respectively). Comparing comparative example
nos. 50, 51, and 52, each of which shows results of combining
soybean oil methyl ester, not distilled and antioxidant composition
of varying amounts (200 ppm to 600 ppm) of TTBP, to example nos.
27-32 of this invention, each of which shows results of combining
soybean oil methyl ester, not distilled and antioxidant composition
of 200 ppm or less of TTBP and PDA, shows that each of example nos.
27-32 has a better RANCIMAT result (8.1 hrs, 9.28 hrs, 8.38 hrs,
7.77 hrs, 6.95 hrs, and 6.46 hrs, respectively) than any of
comparative example nos. 50, 51, or 52 (5.28 hrs, 5.53 hrs, and
5.84 hrs, respectively). In particular, comparing comparative
example no. 50 (with an antioxidant composition of 200 ppm TTBP,
and a RANCIMAT result of 5.28 hrs.) with example no. 28 of this
invention (with an antioxidant composition of 200 ppm TTBP and 200
ppm PDA, and a RANCIMAT result of 9.28 hrs) it can be seen that
this invention provides a substantial benefit. A similar
comparison, based on antioxidant composition of ETHANOX 4703
compared to antioxidant compositions of this invention including
ETHANOX 4703, can be made between comparative example no. 48 and
example nos. 3, 7, 8, and 9 of this invention. Comparative example
no. 47 shows use of 381 ppm PDA as an antioxidant with distilled
biodiesel gives a RANCIMAT result of 6.39 hrs. While some of the
examples of this invention using a distilled biodiesel and an
antioxidant of PDA with a mono or bis-hindered phenolic show a
lower RANCIMAT result, none of these examples use near 381 ppm PDA.
The relatively high cost of PDA, and relatively low cost of
phenolics, makes it beneficial to be able to use smaller amounts of
PDA with a phenolic, in accordance with this invention, and yet
obtain acceptable RANCIMAT results. See, e.g., examples nos. 2 and
3 of this invention where, with a distilled biodiesel, only 200 ppm
PDA is used with a phenolic and RANCIMAT results of 8.76 hrs and
10.52 hrs are obtained. Also, in each of the examples of this
invention using a distilled biodiesel and an antioxidant of PDA and
phenolic that shows a RANCIMAT result lower than 6.39 hrs, the
phenolic in the antioxidant is ETHANOX 4733; the lowest such
RANCIMAT result being 3.87 hrs. Comparing this to comparative
example nos. 42 and 44 (RANCIMAT results of 2.94 hrs and 2.88 hrs),
where ETHANOX 4733 is used with amines not of this invention, shows
improved results with antioxidant compositions of this invention.
Comparative example no. 49 shows use of 200 ppm PDA as an
antioxidant with biodiesel (not distilled) gives a RANCIMAT result
of 9.01 hrs. Comparative example no. 50 shows use of 200 ppm TTBP
as an antioxidant with biodiesel (not distilled) gives a RANCIMAT
result of 5.28 hrs. When a combination of 100 ppm TTBP and 100 ppm
PDA of this invention is used as an antioxidant with biodiesel (not
distilled) a RANCIMAT result of 8.1 hrs is obtained (example no.
27). The result of 8.1 hrs with the TTBP/PDA combination is
significantly better than the 5.28 hrs obtained with the TTBP
alone. Also, the result of 8.1 hrs with the TTBP/PDA combination is
only slightly lower than the 9.01 hrs obtained with the PDA alone
and yet provides a commercially significant cost advantage. While
some of the examples of this invention using a biodiesel (not
distilled) and an antioxidant of PDA with a mono or bis-hindered
phenolic show a lower RANCIMAT result, none of these examples use
near 200 ppm PDA.
TABLE-US-00001 TABLE 1 Antioxidant Composition (ppm Result Example
No. Biodiesel Sample based on Biodiesel) (Hrs) 1 soybean oil methyl
200 ppm ETHANOX 8.76 ester, distilled 4733, 200 ppm PDA 2 soybean
oil methyl 200 ppm PDA, 200 10.52 ester, distilled ppm ETHANOX 4702
3 soybean oil methyl 200 ppm PDA, 200 9.53 ester, distilled ppm
ETHANOX 4703 4 soybean oil methyl 85 ppm ETHANOX 5.85 ester,
distilled 4733, 295 ppm PDA 5 soybean oil methyl 183 ppm ETHANOX
6.91 ester, distilled 4733, 206 ppm PDA 6 soybean oil methyl 296
ppm ETHANOX 5.89 ester, distilled 4733, 98 ppm PDA 7 soybean oil
methyl 318 ppm PDA, 104 9.3 ester, distilled ppm ETHANOX 4703 8
soybean oil methyl 204 ppm PDA, 202 7.88 ester, distilled ppm
ETHANOX 4703 9 soybean oil methyl 105 ppm PDA, 297 6.56 ester,
distilled ppm ETHANOX 4703 10 soybean oil methyl 100 ppm ETHANOX
4.45 ester, distilled 4733, 100 ppm PDA 11 soybean oil methyl 200
ppm ETHANOX 6.5 ester, distilled 4733, 200 ppm PDA 12 soybean oil
methyl 300 ppm ETHANOX 8.35 ester, distilled 4733, 300 ppm PDA 13
soybean oil methyl 150 ppm ETHANOX 3.87 ester, distilled 4733, 50
ppm PDA 14 soybean oil methyl 300 ppm ETHANOX 5.47 ester, distilled
4733, 100 ppm PDA 15 soybean oil methyl 450 ppm ETHANOX 6.78 ester,
distilled 4733, 150 ppm PDA 16 soybean oil methyl 100 ppm ETHANOX
4.34 ester, distilled 4733, 100 ppm PDA 17 soybean oil methyl 200
ppm ETHANOX 6.54 ester, distilled 4733, 200 ppm PDA 18 soybean oil
methyl 300 ppm ETHANOX 8.42 ester, distilled 4733, 300 ppm PDA 19
soybean oil methyl 400 ppm ETHANOX 9.69 ester, distilled 4733, 400
ppm PDA 20 soybean oil methyl 500 ppm ETHANOX 11.19 ester,
distilled 4733, 500 ppm PDA 21 soybean oil methyl 375 ppm ETHANOX
6.15 ester, distilled 4733, 125 ppm PDA 22 soybean oil methyl 375
ppm ETHANOX 6.07 ester, distilled 4733, 125 ppm PDA 23 soybean oil
methyl 100 ppm ETHANOX 7.74 ester, not distilled 4733, 100 ppm PDA
24 soybean oil methyl 200 ppm ETHANOX 9.04 ester, not distilled
4733, 200 ppm PDA 25 soybean oil methyl 150 ppm ETHANOX 6.82 ester,
not distilled 4733, 50 ppm PDA 26 soybean oil methyl 300 ppm
ETHANOX 8.3 ester, not distilled 4733, 100 ppm PDA 27 soybean oil
methyl 100 ppm PDA, 100 8.1 ester, not distilled ppm TTBP 28
soybean oil methyl 200 ppm PDA, 200 9.28 ester, not distilled ppm
TTBP 29 soybean oil methyl 100 ppm PDA, 300 8.38 ester, not
distilled ppm TTBP 30 soybean oil methyl 100 ppm PDA, 100 7.77
ester, not distilled ppm TTBP 31 soybean oil methyl 75 ppm PDA, 75
ppm 6.95 ester, not distilled TTBP 32 soybean oil methyl 50 ppm
PDA, 50 ppm 6.46 ester, not distilled TTBP 33 soybean oil methyl
none 1.57 (comparative) ester, distilled 34 soybean oil methyl none
1.58 (comparative) ester, distilled 35 soybean oil methyl none 1.7
(comparative) ester, distilled 36 soybean oil methyl none 1.58
(comparative) ester, distilled 37 soybean oil methyl none 1.56
(comparative) ester, distilled 38 soybean oil methyl none 1.59
(comparative) ester, distilled 39 soybean oil methyl none 1.61
(comparative) ester, distilled 40 soybean oil methyl none 4.63
(comparative) ester, not distilled 41 soybean oil methyl none 4.49
(comparative) ester, not distilled 42 soybean oil methyl 300 ppm
ETHANOX 2.94 (comparative) ester, distilled 4733, 100 ppm
didecylmethylamine 43 soybean oil methyl 300 ppm ETHANOX 3.6
(comparative) ester, distilled 4702, 100 ppm didecylmethylamine 44
soybean oil methyl 300 ppm ETHANOX 2.88 (comparative) ester,
distilled 4733, 100 ppm dilauryl thiodipropionate 45 soybean oil
methyl 300 ppm ETHANOX 3.87 (comparative) ester, distilled 4702,
100 ppm dilauryl thiodipropionate 46 soybean oil methyl 300 ppm
ETHANOX 4.06 (comparative) ester, distilled 4702, 100 ppm N,N'
disalicylidene propylenediamine 47 soybean oil methyl 381 ppm PDA
6.39 (comparative) ester, distilled 48 soybean oil methyl 471 ppm
ETHANOX 3.14 (comparative) ester, distilled 4703 49 soybean oil
methyl 200 ppm PDA 9.01 (comparative) ester, not distilled 50
soybean oil methyl 200 ppm TTBP 5.28 (comparative) ester, not
distilled 51 soybean oil methyl 400 ppm TTBP 5.53 (comparative)
ester, not distilled 52 soybean oil methyl 600 ppm TTBP 5.84
(comparative) ester, not distilled
[0023] It is to be understood that the reactants and components
referred to by chemical name or formula anywhere in the
specification or claims hereof, whether referred to in the singular
or plural, are identified as they exist prior to being combined
with or coming into contact with another substance referred to by
chemical name or chemical type (e.g., another reactant, a solvent,
or etc.). It matters not what chemical changes, transformations
and/or reactions, if any, take place in the resulting combination
or solution or reaction medium as such changes, transformations
and/or reactions are the natural result of bringing the specified
reactants and/or components together under the conditions called
for pursuant to this disclosure. Thus the reactants and components
are identified as ingredients to be brought together in connection
with performing a desired chemical reaction or in forming a
combination to be used in conducting a desired reaction.
Accordingly, even though the claims hereinafter may refer to
substances, components and/or ingredients in the present tense
("comprises", "is", etc.), the reference is to the substance,
component or ingredient as it existed at the time just before it
was first contacted, combined, blended or mixed with one or more
other substances, components and/or ingredients in accordance with
the present disclosure. Whatever transformations, if any, which
occur in situ as a reaction is conducted is what the claim is
intended to cover. Thus the fact that a substance, component or
ingredient may have lost its original identity through a chemical
reaction or transformation during the course of contacting,
combining, blending or mixing operations, if conducted in
accordance with this disclosure and with the application of common
sense and the ordinary skill of a chemist, is thus wholly
immaterial for an accurate understanding and appreciation of the
true meaning and substance of this disclosure and the claims
thereof.
[0024] While the present invention has been described in terms of
one or more preferred embodiments, it is to be understood that
other modifications may be made without departing from the scope of
the invention, which is set forth in the claims below.
GLOSSARY
[0025] Biodiesel comprises crude biodiesel, distilled biodiesel, or
any individual chemical component of either.
[0026] Crude biodiesel comprises 8 carbon to 22 carbon saturated,
mono-unsaturated, di-unsaturated, or tri-unsaturated methyl ester,
or fatty acid methyl ester derived from a vegetable or animal
source.
[0027] Distilled biodiesel comprises crude biodiesel that has been
subjected to at least one distillation step, e.g., to remove excess
alcohols, residual glycerine, and other impurities, and includes
biodiesel obtained as a specific cut or fraction produced during
the distillation of crude biodiesel.
[0028] TTBP comprises essentially 100%
2,4,6-tri-tert-butylphenol.
* * * * *