Title of Invention

METHOD FOR THE PRODUCTION OF FATTY ACIDS HAVING A LOW TRANS-FATTY ACID CONTENT

Abstract This invention relates to a method of hydrolyzing g]ycera1 fatty acid ester-containing composition. such as a fat and/or an oil, produce fatty acid having a low proportion of trans-isomer feign acid. Specifically, the present invention relates to a process for the hydrolyzing the glycerol fatty acid ester- containing composition under condition resulting in a low proportion of trans-isomer fatty acids.
Full Text WO 2004/111164 PCT/US2004/018586
METHOD FOR THE PRODUCTION OF FATTY ACIDS HAVING A LOW TRANS-
FATTY ACID CONTENT
INVENTORS
Paul D. Bloom
Inmok Lee
Peter Reimers
BACKGROUND
1. Field of the Invention
A method of hydrolyzing fats and oils to produce fatty acids having a low
proportion of trans-isomer fatty acids. Specifically, the present invention relates to a
process for hydrolyzing fats and oils under conditions resulting in a low proportion of
trans-isomer fatty acids.
2. Description of the Related Art
The term "fatty acids" is commonly understood to refer to the carboxylic acids
naturally found in animal fats, vegetable, and marine oils. They consist of long, straight
hydrocarbon chains, often having 12-22 carbon atoms, with a carboxylic acid group at
one end. Most natural fatty acids have even numbers of carbon atoms. Fatty acids
may or may not contain carbon-carbon double bonds. Those without double bonds are
known as saturated fatty acids, while those with at least one double bond are known as
unsaturated fatty acids. The most common saturated fatty acids are palmitic acid (16
carbons) and stearic acid (18 carbons). Oleic and linoieic acid (both 18 carbons) are
the most common unsaturated fatty acids.
Trans fatty acids are unsaturated fatty acids that contain at least one double
bond in the trans isomeric configuration. The trans double bond configuration results in
a greater bond angle than the cis configuration. This results in a more extended fatty
acid carbon chain more similar to that of saturated fatty acids rather than that of cis
unsaturated double bond containing fatty acids. The conformation of the double
bond(s) impacts on the physical properties of the fatty acid. Those fatty acids
containing a trans double bond have the potential for closer packing or aligning of acyl
chains, resulting in decreased mobility; hence fluidity is reduced when compared to fatty
acids containing a cis double bond. Trans fatty acids are commonly produced by the
partial hydrogenation of vegetable oils
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It has long been known that high dietary levels of saturated fatty acids are linked
to increased total and low-density lipoprotein (LDL) cholesterol concentrations. More
recently, however, a number of studies have reported that a diet rich in trans-isomer
fatty acids not only increased LDL concentrations but also decreased high-density
lipoprotein (HDL) cholesterol concentration, resulting in a less favorable overall total
cholesterol/HDL cholesterol ratio (Aro et al, Am. J. Clin. Nutr., 65:1419-1426 (1997);
Judd et al, Am. J. Clin. Nutr., 59:861-868 (1994); Judd et al, Am. J. Clin. Nutr.,
68:768-777 (1998); Louheranta et al, Metabolism 48:870-875 (1999); Mensik and
Katan, N. Engl. J. Med. 323:439-445 (1990); Muller et al, Br. J. Nutr. 80:243-251
(1998);Sundram et al, J. Nutr. 127:514S-520S (1997)). Recent data has further
demonstrated a dose-dependent relationship between trans-isomer fatty acid intake and
the LDL: HDL ratio and the magnitude of this effect is actually greater for trans-isomer
fatty acids compared to saturated fatty acids (Ascherio et al, N. Engl. J Med.
340:1994-1998(1999)).
Naturally occurring fats and oils contain triesters of glycerol and three fatty acids.
Hence, they are referred to chemically as triacylglycerols or, more commonly,
triglycerides. The fat or oil from a given natural source is a complex mixture of many
different triacylglycerols. Vegetable oils consist almost entirely of unsaturated fatty
acids, while animal fats contain a much larger percentage of saturated fatty acids. Fats
and oils are used in a wide variety of products, such as soaps and surfactants,
lubricants, and in a variety of other food, agricultural, industrial, and other personal care
products.
Triacylglycerols, like all esters, can by hydrolyzed to yield their carboxylic acids
and alcohols. The reaction products produced by the hydrolysis of a fat or oil molecule
are one molecule of glycerol and three molecules of fatty acids. This reaction proceeds
via stepwise hydrolysis of the acyl groups on the glyceride, so that at any given time,
the reaction mixture contains not only triglyceride, water, glycerol, and fatty acid, but
also diglycerides and monoglycerides.
Currently, the most commonly used commercial process for hydrolyzing fats and
oils is a high-temperature steam treatment method known as the Colgate-Emery Steam
Hydrolysis Process (Brady, C., L. Metcalfek, D. Slaboszewski, and D. Frank, JAOCS,
65:917-921 (1988)). This method, and modifications thereof, use a countercurrent
reaction of water and fat under high temperatures ranging from 240°C to 315°C and
high pressures in the range of 700 to 750 PSIG. Presently, the Colgate-Emery process
is the most efficient and inexpensive method for large-scale production of saturated fatty
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acids from fats and oils. In this method, a tower is used to mix the fat and water to
increase the efficiency of the hydrolysis reaction. The fat is introduced from the bottom
of a tower with a high pressure feed pump. Water is introduced from near the top of the
tower at a ratio of 40-50% of the weight of the fat. As the fat rises though the
descending water, a continuous oil-water interface is created. It is at this interface that
the hydrolysis reaction occurs. Direct injection of high pressure steam raises the
temperature to approximately 260°C and the pressure is maintained at 700-715 PSIG.
The increased pressure causes the boiling point of the water to increase, allowing for
the use of higher temperatures, which results in the increase of the solubility of the
water in the fat. The increased solubility of water provides for a more efficient
hydrolysis reaction. This continuous, countercurrent, high pressure process allows fora
split yield of 98-99% efficiency in 2-3 hours (Sonntag, JAOCS 56: 729A-732A (1979)).
Further purification of the fatty acid product obtained by this method is often
accomplished by means such as distillation.
However, due to the extreme reaction conditions, this process often leads to
extensive degradation of the produced fatty acids. For example, the Colgate-Emery
method has not been shown to be effective in splitting heat sensitive triglycerides
containing conjugated double bonds, hydroxy-containing fats and oils like castor oil, fish
oils containing polyunsaturated acids and soybean oils high in unsaturated fats due the
formation of by-products such as trans-isomer fatty acids and the degradation of the
unsaturated fatty acids at high temperatures (Sonntag, JAOCS 56: 729A-732A (1979)).
Therefore, the production of fatty acids from vegetable oils (e.g., soya, corn and
peanut), which are generally high in unsaturated fats, is not recommended by this
method.
Some sectors of industry have used other methods of hydrolysis to avoid the by-
product formation and unsaturated fat degradation associated with the high pressure-
high temperature hydrolysis of unsaturated fats and oils. These include the hydrolysis
of unsaturated oils by splitting them with a base followed by acidulation or by enzymatic
hydrolysis. However, none of these methods have shown split yields comparable to the
Colgate-Emery process under similar time conditions.
In light of the limitations of the current methods used for the hydrolysis of
unsaturated fats and oils, a need in the art exists for an efficient method of non-catalytic
hydrolysis suitable for unsaturated fats and oils which produces fatty acid products with
a low percentage of trans-isomer fatty acids.
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Moreover, the U.S. Food and Drug Administration has initiated the process of
requiring food labels to include the trans-isomer fatty acid contents of food. As such,
there is an incentive for food manufacturers to decrease the trans-isomer fatty acid
content of their products. Thus, a need has developed for methods of hydrolysis of
unsaturated fats and oils that provide for the production of fatty acids with a low
proportion of trans-isomer fatty acids for use as food products.
The present invention addresses these needs by providing a method of
hydrolyzing fats and oils high in unsaturated fat whereby the fatty acid products have a
low trans-isomer fatty acid content suitable for use in the food industry.
BRIEF SUMMARY OF THE INVENTION
Methods are provided for production of fatty acids by the hydrolysis of a glycerol
fatty acid ester-containing composition, such as a fat and/or an oil, under reaction
conditions that result in the production of fatty acid products having a low proportion of
trans-isomer fatty acids.
The low trans-isomer fatty acid product typically is further processed to first
separate the oil phase from the aqueous phase and removing fatty acids from the oil
phase, for example, by distillation. The low trans-isomer fatty acid product can then be
used as a substrate for the production of 1,3-diacylglycerides.
The removal of the fatty acids from the oil phase leaves a glycerol fatty acid
ester-containing residue phase that can be recycled for use as a starting material for
subsequent hydrolysis reactions, typically be mixing the residue phase with additional
glycerol fatty acid ester-containing composition.
Also provided are low trans-isomer fatty acids produced by the hydrolysis of fats
and/or oils high in unsaturated fats.
In one embodiment, the low trans-isomer fatty acids are used in the production of
food products such as cooking oils.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a graph showing the increase in formation of trans-isomer fatty acids
at various temperatures and various times. 280 g RBD (refined/bleached/deodorized)
of soy oil (0.8% trans-isomer content) was reacted with 420 g of water at 220°C (black
stars), 225°C (gray stars), 230°C (white triangles), 235°C (gray squares), and 250°C
(black diamonds) for 0-6 hours. The trans-isomer formation was determined by gas
chromatography. This data shows that trans-isomer formation is dependent on reaction
temperature and time.
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Figure 2 is a graph showing the split ratio (% fatty acid formed) at various
temperatures and various times. 280 g of RBD (refined/bleached/deodorized) soy oil
(0.8% trans-isomer content) was reacted with 420 g of water at 225°C (gray stars),
230°C (white triangles), 235°C (gray squares), and 250°C (black diamonds) for 0-6
hours. The degree of hydrolysis (split ratio) was determined by titration of fatty acids
with potassium hydroxide (KOH). This data shows that an efficient hydrolysis reaction
can be achieved at temperatures below 300°C in a reasonable reaction time.
DETAILED DESCRIPTION
A novel method is provided for the production of fatty acids having low trans-
isomer fatty acid content through the hydrolysis of glycerol fatty acid ester-containing
compositions, such as fats and/or oils.
As used herein, the term "hydrolysis" refers to the separation of a glycerol fatty
acid ester-containing composition, such as a fat or oil starting material, into its fatty acid
and glycerin components by reacting the starting material with water. In a preferred
embodiment, this reaction is non-catalytic.
The hydrolysis reaction may be conducted in a batch, continuous or semi-
continuous method depending on the needs of the user.
Batch hydrolysis methods refer to the method of taking all the reactants at the
beginning of the hydrolysis reaction and processing them according to a predetermined
course of reaction during which no material is fed into or removed from the batch
reactor (Perry's Chemical Engineers' Handbook, p. 4-25, Sixth Edition (1984)).
Continuous hydrolysis methods refer to methods in which reactants are
introduced to the reaction and products are simultaneously withdrawn from the reaction
in a continuous manner. This method is commonly used in large-scale production
facilities (Perry's Chemical Engineers' Handbook, p. 4-25, Sixth Edition (1984)).
Semi-continuous hydrolysis methods refer to methods that are neither batch nor
continuous in nature. In one embodiment, some of the reactants are changed at the
beginning, and the remaining reactants are introduced and the reaction progresses. In
other embodiments, the reactions products are removed continuously from the reactor
(Perry's Chemical Engineers' Handbook, p. 4-25, Sixth Edition (1984)).
The hydrolysis reaction may incorporate an agitation or countercurrent flow
method to increase the efficiency of the reaction. This can be done either by
mechanical means or by the countercurrent method described in the Colgate-Emery
method.
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The amount of water used in the hydrolysis reaction is based upon the weight of
the starting material. One embodiment of the invention uses a minimum of three moles
of water for every one mole of starting material. In a preferred embodiment, the ratio of
water to starting material is 1.5 g water to 1 g starting material.
The hydrolysis reaction can be performed over a temperature range of about
200°C to about 300°C. A preferred temperature range for hydrolysis is from about
220°C to about 250°C. A more preferred temperature range for hydrolysis is from about
225°C to about 235°C. An even more preferred temperature for hydrolysis is about
230°C.
The hydrolysis reaction can be performed in a batch method over a time range of
about 0 hours to about 6 hours. A preferred time range for batch hydrolysis is from
about 2 hours to about 4 hours. A more preferred time for batch hydrolysis is about 3
hours. However, the semi-continuous and continuous methods allow for perpetual
processing due to the continuous introduction of starting materials and water to the
reaction.
The terms "split yield" and "split ratio" are used interchangeably and refer to the
percentage of free fatty acids produced by the hydrolysis reaction. As used herein, the
terms refer to the fatty acid content of the oil phase.
The phrases "high split yield" or "efficient hydrolysis" are interchangeable and
defined as split yields greater that 80%. More preferably, the split yield produced by the
process of the invention is greater than 90%, more preferably greater than 91 %, more
preferably greater than 92%, more preferably greater than 93%, more preferably greater
than 94%, more preferably greater than 95%, more preferably greater than 96%, more
preferably greater than 97%, more preferably greater than 98%, more preferably greater
than 99%.
Fatty acids with a low trans-isomer fatty acid content can also be obtained with
low split yields. For example, fatty acids with a low trans-isomer fatty acid content are
produced by a hydrolysis reaction with a split yield less than 80%, with a split yield less
than 70%, with a split yield less than 60%, with a split yield less than 40%, or with a split
yield less than 20%.
The starting materials that may be used in this invention vary widely. For
purposes herein, starting materials include one or more refined or unrefined, bleached
or unbleached and/or deodorized or non-deodorized fats or oils. The fats or oils can
comprise a single fat or oil or combinations of more than one fat or oil. Likewise, the
fats or oils either can be saturated, mono-unsaturated or poly-unsaturated or any
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combination thereof. The term "saturated" refers to the presence of carbon-carbon
double bonds within the hydrocarbon chain. In a preferred embodiment, the starting
material is mono-unsaturated or poly-unsaturated vegetable oil. In a particularly
preferred embodiment, the starting material is a poly-unsaturated vegetable oil.
The one or more unrefined and/or unbleached fats or oils can comprise butterfat,
cocoa butter, cocoa butter substitutes, illipe fat, kokum butter, milk fat, mowrah fat,
phulwara butter, sal fat, shea fat, borneo tallow, lard, lanolin, beef tallow, mutton tallow,
talfow or other animal fat, canola oil, castor oil, coconut oil, coriander oil, corn oil,
cottonseed oil, hazlenut oil, hempseed oil, linseed oil, mango kernel oil, meadowfoam
oil, neat's foot oil, olive oil, palm oil, palm kernel oil, palm olein, palm stearin, palm
kernel olein, palm kernel stearin, peanut oil, rapeseed oil, rice bran oil, safflower oil,
sasanqua oil, soybean oil, sunflower seed oil, tall oil, tsubaki oil, vegetable oils, marine
oils which can be converted into plastic or solid fats such as menhaden, candlefish oil,
cod-liver oil, orange roughy oil, pile herd, sardine oil, whale and herring oils, or
combinations thereof.
The phrase "high in unsaturated fats" includes fats and oils, or mixtures thereof,
with an iodine value of greater than 110 as determined by the Wijs method. The term
"iodine value" is defined as a measure of the total number of unsaturated double bonds
present in a fat or oil. In a preferred embodiment, the fat or oil subjected to hydrolysis
according to the present invention has an iodine value of above 120, more preferably
above 130, more preferably above 135, and more preferably above 140.
The term "fatty acid" as used herein is applied broadly to carboxylic acids which
are found in animal fats, vegetable and marine oils. They can be found naturally in
saturated, mono-unsaturated or poly-unsaturated forms. The natural geometric
configuration of fatty acids is cis-isomer configuration. The cis-isomer configuration
contributes significantly to the liquidity of these acids.
The term "trans-isomer fatty acids" is defined as unsaturated fatty acids that
contain at least one double bond in the trans isomeric configuration. As used herein,
the phrases "low proportion of trans-isomer fatty acid" or "low trans-isomer fatty acid
content" mean that the proportion of trans-isomer fatty acids found in the fatty acid
product of the hydrolysis reaction of the present invention is less than 6% of the total
fatty acid composition of the fatty acid product. In a preferred embodiment, the trans-
isomer fatty acid content of the fatty acids produced by the hydrolysis of the invention is
less than 5% of the total fatty acid product, more preferably less than 4%, more
preferably less than 3%, more preferably less than 2%, more preferably less than 1.5%.
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The term fatty acid product" as used herein refers to the product of the
hydrolysis reaction that comprises the free fatty acid component of the starting material.
In a preferred embodiment, the process of the invention will yield a fatty acid product
with less than a 3% increase in trans-isomer fatty acid content as compared to the
trans-isomer fatty acid content of the starting material, more preferably less than 2.5%
increase, more preferably less than 2% increase, more preferably less than 1.5%
increase, more preferably less than 1% increase.
In another embodiment, the process of the invention further includes separating
the free fatty acids (contained in the oil phase) from the reaction mixture (aqueous
phase). As used herein, the term "oil phase" refers to the non-aqueous phase of the
product of the hydrolysis reaction. Initially, the oil phase must be separated from the
aqueous phase. Common methods of separation include centrifugation, distillation or
settling. Upon separating the oil and aqueous phases, the free fatty acids are further
separated from the other components of the oil phase. This is accomplished by
distilling the oil phase, which results in the production of a distillate (containing free fatty
acids) phase and a residue phase.
In another embodiment, the residue phase of the distillation process, comprised
mainly of mono-acylglycerides, di-acylgiycerides and tri-acylglycerides, may be further
processed to extract additional fatty acids. This further processing includes recycling
the residue product back through the hydrolysis process.
In another embodiment, the fatty acid products of this invention can be further
processed to produce low saturated, low trans-isomer fatty acid. This further
processing includes coupling the hydrolysis method described herein with a method for
removing saturated fatty acids via low temperature crystallization. More particularly, the
process includes the mixing of the fatty acid product with a polyglycerol ester crystal
modifier and subjecting the mixture to winterization in order to separate saturated fatty
acids from unsaturated fatty acids. As used herein, the term "winterization" refers to the
process of cooling oil to low temperatures until the high melting point molecules form
solid particles large enough to be filtered out. Winterization is a specialized form of the
overall process of fractional crystallization.
In a particularly preferred embodiment, the fatty acids produced by the methods
of the present invention are used to make 1,3-diacylglycerol. Specifically, the fatty acids
products of the hydrolysis reaction of the present invention are treated with an enzyme,
such as a lipase, which catalyzes esterification or transesterification of the terminal
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esters in the 1 and 3 positions of a glyceride. The products of esterification or
transesterification may be further used in the production of food products.
In an alternative embodiment, the fatty acids produced by the methods of the
present invention are further processed by hydrogenation. As used herein,
hydrogenation refers to the addition of hydrogen to double bonds of unsaturated fatty
acids. This reaction is carried out by reacting the fatty acid product with gaseous
hydrogen at elevated temperature and pressure.
In a further embodiment, the present invention is directed to a fatty acid
composition having a low proportion of trans-isomer fatty acids prepared by the
methods of the invention.
In another embodiment, the present invention is directed to a cooking oil
containing the low trans-isomer fatty acid compositions of the present invention.
In yet another embodiment, the present invention is directed to foods containing
the low trans-isomer fatty acid compositions of the present invention.
EXAMPLES
The examples described below show that starting material high in unsaturated
fats can be hydrolyzed non-catalytically to produce a fatty acid product with low trans-
isomer fatty acid content. The following examples are illustrative only and are not
intended to limit the scope of the invention as defined by the appended claims.
Example 1
280 g of RBD (refined/bleached/deodorized) soy oil (0.8 trans-isomer content)
and 420 g of water were reacted in a 1-L high pressure reactor with agitation of 1050
rpm for the given temperature and given times. The trans-isomer fatty acid content was
determined by gas chromatography analysis.
Figure 1 summarizes the results. After 6 hours at 250 C, the trans-isomer fatty
acid content was 6% (black diamonds). After 6 hours at 235 C, the trans-isomer fatty
acid content was 2.3% (gray squares). After 6 hours at 230 C, the trans-isomer fatty
acid content was 2.1 % (white triangles). After 6 hours at 225 C, the trans-isomer fatty
acid content was 1.8% (gray stars). The results from this example demonstrate that by
controlling the temperature and the time of the hydrolysis reaction, a fatty acid product
can be obtained with low trans-isomer fatty acid content.
Example 2
280 g of RBD (refined/bleached/deodorized) soy oil (0.8% trans-isomer content)
and 420 g of water were reacted in a 1-L high pressure reactor with agitation of 1050
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rpm for the given temperature and given times. The split yield was determined by
titration of fatty acids with potassium hydroxide.
Figure 2 summarizes the results. After 3 hours at 250°C, the split yield was 95%
(black diamonds). After 3 hours at 235°C, the split yield was 95% (gray squares). After
3 hours at 230°C, the split yield was 93% (white triangles). After 3 hours at 225°C, the
split yield was 90% (gray stars). The results demonstrate that efficient hydrolysis can
occur at temperatures beiow 300°C.
Example 3
The following example demonstrates the ability to further process the fatty acid
product of the presently claimed hydrolysis reaction by recycling the residue portion of
the fatty acid product after it has been purified by evaporation. 280 g of RBD
(refined/bleached/deodorized) soy oil (0.8% trans-isomer content) was reacted with 420
g of water in a 1-L high pressure reactor. After a 3 hour reaction at 230 C, the split ratio
and trans-isomer level were determined to be 92% and 2.1%, respectively. The upper
phase of the hydrolysis reaction (fatty acid portion) was separated and purified by
distillation. The distillate and residue were 87 parts and 13 parts, respectively. The
distillate was 99% pure fatty acid. The residue was recycled back to the fat-splitting
step for 5 cycles. During the 5 recycling steps, the average split ratio was 92%. There
was no significant change in fatty acid composition, including trans-isomer formation,
during the 5 recycles.
Example 4
RBD (refined/bleached/deodorized) soy oil (0.8% trans-isomer content) and
water were reacted in a 1-Gal high pressure reactor at 230°C and samples were drawn
every 15 minutes as oil and water were fed into the reactor continuously for 30 hours.
The upper phase of the withdrawn sample was separated and subjected to distillation
for recovery of the fatty acid product. The residue portion was recycled back into the
reactor as a part of the oil feed. The split ratio and trans-isomer fatty acid content in the
final fatty acid products were determined, the average split ratio was about 80% and the
trans-isomer content was 1.8%.
All publications mentioned above are herein incorporated by reference in their
entirety.
While the foregoing invention has been described in some detail for purposes of
clarity and understanding, it will be appreciated by one skilled in the art form a reading
of this disclosure that various changes in form and detail can be made without departing
from the true scope of the invention and appended claims.
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We claim:
1. A process for producing fatty acids comprising hydrolyzing a glycerol fatty
acid ester-containing composition under reaction conditions resulting in fatty acids
having a low proportion of trans-isomer fatty acids.
2. The method of claim 1, wherein the reaction conditions are time of
hydrolysis and temperature of hydrolysis.
3. The method of claim 2, wherein the reaction condition of temperature is
maintained at a temperature not exceeding 300°C during said process.
4. The method of claim 2, wherein the temperature is maintained within the
range of 220°C to 250°C during the hydrolysis.
5. The method of claim 2, wherein the temperature is about 230°C during the
hydrolysis.
6. The method of claim 2, wherein the glycerol fatty acid ester-containing
composition is hydrolyzed for 1 to 6 hours.
7. The method of claim 2, wherein the glyceroi fatty acid ester-containing
composition is hydrolyzed for 2 to 4 hours.
8. The method of claim 2, wherein the glyceroi fatty acid ester-containing
composition is hydrolyzed for about 3 hours.
9. The method of claim 1, wherein the glycerol fatty acid ester-containing
composition comprises a mixture of saturated and unsaturated fats or oils.
10. The method of claim 9, wherein the glyceroi fatty acid ester-containing
composition comprises a vegetable oil.
11. The method of claim 10, wherein the vegetable oil is selected from the
group consisting of canola oil, castor oil, coconut oil, coriander oil, corn oil, cottonseed
oil, hazelnut oil, olive oil, palm oil, peanut oil, rapeseedoil, rice bran oil, safflower oil,
soybean oil and sunflower seed oil.
12. The method of claim 10, wherein the vegetable oil is soybean oil.
13. The method of claim 1, wherein the glyceroi fatty acid ester-containing
composition comprises a mixture of unsaturated fats.
14. The method of claim 13, wherein the glycerol fatty acid ester-containing
composition comprises a vegetable oil.
15. The method of claim 14, wherein the vegetable oil is selected from the
group consisting of canola oil, castor oil, coconut oil, coriander oil, corn oil, cottonseed
oil, hazelnut oil, olive oil, palm oil, peanut oil, rapeseed oil, rice bran oil, safflower oil,
soybean oil and sunflower seed oil.
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16. The method of claim 14, wherein the vegetable oil is soybean oil.
17. The method of claim 1, wherein the fatty acid product has a trans-isomer
fatty acid content of less than 6%.
18. The method of claim 17, wherein the fatty acid product has a trans-isomer
fatty acid content of less than 5%.
19. The method of claim 17, wherein the fatty acid product has a trans-isomer
fatty acid content of less than 4%.
20. The method of claim 17, wherein the fatty acid product has a trans-isomer
fatty acid content of less than 3%.
21. The method of claim 17, wherein the fatty acid product has a trans-isomer
fatty acid content of less than 2%.
22. The method of claim 17, wherein the fatty acid product has a trans-isomer
fatty acid content of less than 1.5%.
23. The method of claim 1, which results in a high split yield.
24. The method of claim 23, wherein the high split yield is greater than 80%.
25. The method of claim 23, wherein the high split yield is greater than 90%.
26. The method of claim 23, wherein the high split yield is greater than 91 %.
27. The method of claim 23, wherein the high split yield is greater than 92%.
28. The method of claim 23, wherein the high split yield is greater than 93%.
29. The method of claim 23, wherein the high split yieid is greater than 94%.
30. The method of claim 23, wherein the high split yield is greater than 95%.
31. The method of claim 23, wherein the high split yield is greater than 96%.
32. The method of claim 23, wherein the high split yield is greater than 97%.
33. The method of claim 23, wherein the high split yield is greater than 98%.
34. The method of claim 23, wherein the high split yield is greater than 99%.
35. The method of claim 1, wherein the fatty acid product has a less than 3%
increase in trans-isomer fatty acid content as compared to the glycerol fatty acid ester-
containing composition.
36. The method of claim 35, wherein the fatty acid product has a less than
2.5% increase in trans-isomer fatty acid content as compared to the glycerol fatty acid
ester-containing composition.
37. The method of claim 35, wherein the fatty acid product has a less than 2%
increase in frans-isomer fatty acid content as compared to the glycerol fatty acid ester-
containing composition.
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38. The method of claim 35, wherein the fatty acid product has a less than
1.5% increase in trans-isomer fatty acid content as compared to the glycerol fatty acid
ester-containing composition.
39. The method of claim 35, wherein the fatty acid product has a less than 1%
increase in trans-isomer fatty acid content as compared to the glycerol fatty acid ester-
containing,
40. The method of claim 1, wherein the reaction conditions are controlled to
reduce thermal degradation of the fat and oil glycerol fatty acid ester-containing
composition.
41. The method of claim 1, wherein the hydrolysis is carried out in a batch
reactor.
42. The method of claim 1, wherein the hydrolysis reaction is carried out in a
semi-continuous reactor.
43. The method of claim 1, wherein the hydrolysis reaction is carried out in a
continuous reactor.
44. The method of claim 1, wherein agitation is used to increase the efficiency
of the hydrolysis reaction.
45. The method of claim 44, wherein the agitation is by mechanical means.
46. The method of claim 44, wherein the agitation is by countercurrent flow.
47. The method of claim 1, further comprising separating the fatty acid product
into an oil phase and an aqueous phase.
48. The method of claim 47, wherein the oil phase comprises a fatty acid with
low trans-isomer fatty acid content.
49. The method of claim 47, wherein the separation is by distillation.
50. The method of claim 49 in which the distillation is performed under a
vacuum.
51. The method of claim 47, wherein the separation is by centrifugation.
52. The method of claim 47, wherein the separation is by settling.
53. The method of claim 47, further comprising distilling the oil phase to yield
a distillate comprising free fatty acids and a residue phase comprising free fatty acids,
mono-acylglycerides, di-acylglycerides, and tri-acylglycerides.
54. The method of claim 53, wherein processing is conducted in a batch
reactor.
55. The method of claim 53, wherein processing is conducted in a continuous
reactor.
13

WO 2004/111164 PCT/US2004/018586
56. The method of claim 53, wherein processing is conducted in a semi-
continuous reactor.
57. The method of claim 53, further comprising hydrolyzing the residue phase
under reaction conditions resulting in fatty acids having a low proportion of trans-isomer
fatty acids.
58. The method of claim 57, wherein, prior to hydrolyzing the residue phase,
the residue phase is mixed with additional glycerol fatty acid ester-containing
composition.
59. The method of claim 57, wherein the hydrolysis is conducted in a batch
reactor.
60. The method of claim 57, wherein the hydrolysis is conducted in a
continuous reactor.
61. The method of claim 57, wherein the hydrolysis is conducted in a semi-
continuous reactor.
62. The method of claim 1, further comprising winterizing the hydrolyzed fatty
acid product to produce an unsaturated fatty acid product having low trans-isomer
content.
63. The method of claim 62, wherein the winterizing comprises:

(a) mixing the fatty acid product with a polyglycerol ester crystal modifier;
(b) cooling the mixture until saturated free fatty acids form solid particles; and
(c) removing the solid particles from the mixture.

64. The method of claim 62, wherein the winterizing is conducted in a batch
reactor.
65. The method of claim 62, wherein the winterizing is conducted in a
continuous reactor.
66. The method of claim 62, wherein the winterizing is conducted in a semi-
continuous reactor.
67. The method of claim 1, further comprising esterifying one of glycerol and a
mono-acylglyceride with the fatty acid product to produce a 1,3-diacylglyceride.
68. The method of claim 67, wherein the esterification is enzymatic.
69. The method of claim 67, wherein a lipase is used in the enzymatic
esterification.
70. The method of claim 67, wherein the esterification is conducted in a batch
reactor.
14

WO 2004/111164 PCT/US2004/018586
71. The method of claim 67, wherein the esterification is conducted in a
continuous reactor.
72. The method of claim 67, wherein the esterification is conducted in a semi-
continuous reactor.
73. A fatty acid composition having low trans-isomer fatty acid content
produced by the method of claim 1.
74. The fatty acid composition of claim 73, wherein the low trans-isomer fatty
acid composition is used in the production of a food product.
75. A fatty acid composition having a low trans-isomer fatty acid content
produced by the method of claim 53.
76. The fatty acid composition of claim 75, wherein the low trans-isomer fatty
acid composition is used in the production of a food product.
77. A fatty acid composition having a low trans-isomer fatty acid content
produced by the method of claim 61.
78. The fatty acid composition of claim 77, wherein the low trans-isomer fatty
acid composition is used in the production of a food product.
79. A 1,3-diacylglyceride composition produced by the method of claim 67.
80. The 1,3-diacylglyceride composition of claim 79, wherein the 1,3-
diacylglyceride composition is used in the production of a food product.
81. A cooking oil comprising low trans-isomer fatty acids produced by the
method of claim 1.
82. A food product comprising low trans-isomer fatty acids produced by the
method of claim 1.
15

This invention relates to a method of hydrolyzing g]ycera1 fatty acid ester-containing composition. such as a fat
and/or an oil, produce fatty acid having a low proportion of trans-isomer feign acid. Specifically, the present invention relates to
a process for the hydrolyzing the glycerol fatty acid ester- containing composition under condition resulting in a low proportion of
trans-isomer fatty acids.

Documents:

02209-kolnp-2005-abstract.pdf

02209-kolnp-2005-claims.pdf

02209-kolnp-2005-description complete.pdf

02209-kolnp-2005-drawings.pdf

02209-kolnp-2005-form 1.pdf

02209-kolnp-2005-form 3.pdf

02209-kolnp-2005-form 5.pdf

02209-kolnp-2005-international publication.pdf

2209-kolnp-2005-assignment.pdf

2209-KOLNP-2005-CORRESPONDENCE.pdf

2209-kolnp-2005-examination report.pdf

2209-kolnp-2005-form 18.pdf

2209-KOLNP-2005-FORM-27.pdf

2209-kolnp-2005-gpa.pdf

2209-kolnp-2005-intenational publication.pdf

2209-kolnp-2005-international search report.pdf

2209-kolnp-2005-others.pdf

2209-kolnp-2005-pct priority document notification.pdf

2209-kolnp-2005-pct request form.pdf

2209-kolnp-2005-petition under rule 137.pdf

2209-kolnp-2005-reply to examination report.pdf


Patent Number 242870
Indian Patent Application Number 2209/KOLNP/2005
PG Journal Number 38/2010
Publication Date 17-Sep-2010
Grant Date 16-Sep-2010
Date of Filing 08-Nov-2005
Name of Patentee ARCHER-DANIELS-MIDLAND COMPANY
Applicant Address 4666 FARIES PARKWAY, DECATUR, IL 62526 UNITED STATES OF AMERICA
Inventors:
# Inventor's Name Inventor's Address
1 BLOOM, PAUL, D. 4005 BAY VIEW DRIVE, DECATUR, IL 62521 UNITED STATES OF AMERICA
2 RIEMERS, PETER 1307 RIDGEPOITE DRIVE, MONTICELLO, IL 61857 UNITED STATES OF AMERICA
3 LEE, INMOK 2320 BOILING SPRINGS ROAD DECATUR, IL 62526 UNITED STATES OF AMERICA
PCT International Classification Number C11C 1/04
PCT International Application Number PCT/US2004/018586
PCT International Filing date 2004-06-10
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 60/477,043 2003-06-10 U.S.A.