GLYCERIDES AND FATTY ACID MIXTURES AND METHODS OF USING SAME
Cross-Reference to Related Applications
None.
Statement Regarding Federally Sponsored Research or Development
Not Applicable.
Background of the Invention
This invention relates generally to methods and compositions useful in green
technologies. More specifically, the present invention relates to glycerides and fatty acid
mixtures derived from ethanol processes as co-products or by-products. These mixtures can be
applied in numerous applications. One application is beneficiation, a method of separating useful
matter from waste, Another application is dewatering, separating water from a material. Other
applications are selected from a list comprising of lubrication fluid, rolling oil, hydraulic fluids,
antifoaxns, defoamers, drilling fluid, coating oil, fire-resistance fluid, bulk density control, coal
bulk density control, and dust control.
As described for example in US Patents 7,624,878 and 7,837,891 B2, and US
Patent Application 12/706091, beneficiation uses the difference in the hydrophobicity of the
respective components. During this process, the mineral ore is comminuted to a certain small
size and slurried with water. The slurry is introduced into a flotation apparatus purged with air.
The air preferentially attaches to the hydrophobic particles of the slurry, making them float to the
top of the apparatus. The floated particles are collected, dewatered, and accumulated as a
sellable final product. The hydrophilic particles tend to migrate to the bottom of the contact
vessel from where they can be removed as tailings and processed into waste impoundments, in
other processes, such as reverse flotation, the sellable final product may migrate to the bottom.
To facilitate beneficiation, several types of conventional reagents are used such as
frothers, collectors, promoters and conditioners. Nevertheless, these reagents can be expensive

and toxic thereby reducing the cost-effectiveness of the beneficiation processes, Diesel fuel, a
petroleum-based fuel such as kerosene or #2 fuel oil, is a common benefioiation composition; it
is toxic and is derived from non-renewable resource. Contrarily, the present invention is non-
hazardous and is derived from renewable resources; it can be used to replace diesel fuel.
It is therefore novel, useful and non-obvious desirable to provide and utilize cost-
effective, non-hazardous, and effective beneflciation compositions. The art described in this
section is not intended to constitute an admission that any patent, publication or other
information referred to herein is "Prior Art" with respect to this invention, unless specifically
designated as such. In addition, this section should not be construed to mean that a search has
been made or that no other pertinent information as defined in 37 CPR § 1.56(a) exists.
Brief Summary of the Invention
At least one embodiment of the invention is directed to a method of separating a
first material from a second material. The method comprises the steps of: (1) mixing the first
material and the second material in a slurry with a beneficiation composition, (2) providing air
bubbles in the slurry to form bubble-particle aggregates with the first material, and (3) allowing
the bubble-particle aggregates to be separated from the second material. The beneficiation
composition comprises at least one glyceride and fatty acid mixtures extracted from an ethanol
process,
The glycerides and fatty acid mixtures (GFA) may contain from 5 percent by
weight to 25 percent by weight free fatty acids. The glycerides and fatty acid mixtures may
comprise one or more component selected from a list of linoleic acid, phytostcrols,
hydroxycinnamatesteryl esters, lutein, and zeaxanthin. The glyceride and fatty acid mixtures
may be extracted from the thin stiliage of a dry mill corn ethanol plant or from the distillers
grains and solubles of a dry mill com ethanol plant. The hydroxycinnamate steryl esters

concentration may range from 0.3 to 0.5 weight percent. The tocopherols concentration may be
less than 150 mg per 100 g of glycerides and fatty acid mixtures. In an embodiment the
tocopherols' concentration is 150 mg per 100 g of glycerides and fatty acid mixtures or less.
The fatty glyceride and fatty acid mixtures may be applied as an emulsion. The
glycerides and fatty acid mixtures may be combined with collectors and/or frothers. At least a
portion (up to 100%) of the glycerides and fatty acid mixtures may be extracted from an ethanoi
process. The glycerides and fatty acid mixtures may further comprise one or more component
selected from a list of linoleic acid, phytosierols, tocopherols, hydroxycinnamatesteryl esters,
lutein, zeaxanthin, carotenoids, and any combination thereof. The glyceride and fatty acid
mixtures may be extracted from the thin stiliage of a dry mill corn ethanoi plant or from the
distillers grains and solubles of a dry mill corn ethanoi plant. The hydroxycinnamate steryl esters
concentration may be within the range of 0.3 to 0.5 weight percent. The tocopherols
concentration may be less than 150 mg per 100 g of glycerides and fatty acid mixtures
Additional features and advantages are described herein, and will be apparent
from, the following Detailed Description.
Detailed Description of the Invention
The following definitions are provided, to determine how terms used in this
application, and in particular how the claims, are to be construed. The organization of the
definitions is for convenience only and is not intended to limit any of the definitions to any
particular category.
For purposes of this application the definition of these terms is as follows:
"Beneficiation" means separating useful matter from waste, particularly
hydrophobic substances from hydrophilic substances. Suitable processes for accomplishing this
include, but are not limited to, flotation, reverse flotation and similar technologies.

"Glycerides and fatty acid mixtures" means mixtures extracted from an ethanoJ
process comprising both glycerides and fatty acid.
In the event that the above definitions or a description stated elsewhere In this
application is inconsistent with a meaning (explicit or implicit) which is commonly used, in a
dictionary, or stated in a source incorporated by reference into this application, the application
and the claim terms in particular are understood to be construed according to the definition or
description in this application, and not according to the common definition, dictionary definition,
or the definition that was incorporated by reference. In light of the above, in the event that a term
can only be understood if it is construed by a dictionary, if the term is defined by the Kirk-
Othmer Encyclopedia of Chemical Technology, 5th Edition, (2005), (Published by Wiley, John &
Sons, Inc.) this definition shall control how the term is to be defined in the claims.
In at least one embodiment, the invention provides a method of separating a first
material from a second material. For example, the method can comprise mixing the first material
and the second material within a slurry with a beneficiation composition. The beneficiation
composition can comprise one or more glycerides and fatty acid mixtures derived from an
ethanol process. Air bubbles can be provided in the slurry to form bubble-particle aggregates
with the first material and the bubble-particle aggregates can be allowed to be separated from the
second material.
In at least one embodiment, the glycerides and fatty acid mixtures can be
generated from an ethanol process. In an ethanol process, the extraction of the glycerides and
fatty acid mixtures can be referred to as corn oil extraction. One method of extracting corn oil is
through recovery from the stillage and/or the distillers grains and solubles produced by a dry corn
ethanol plant. In an embodiment, the glycerides and fatty acid mixtures contains about 5 to 25
weight percent free iatty acids. In anodier embodiment the GFA contains 5% free fatty acids by
weight or greater. Linoleic acid is typically die predominant fatty acid. The glycerides and fatty

one or more components selected from a list comprising of phytosterols, tocopherols,
hydroxycinnamate steryl esters, lutein, ze&xanthin, and carotenoids,
The glycerides and fatty acid mixtures (GFA) were surprisingly found to be
effective as reagents for use in beneficiation technologies such as, for example, flotation
processes. In addition, these glycerides and fatty acid mixtures are generally environmentaliy
benign and non-hazardous. The glycerides and fatty acid mixtures are also non-combustible and
can provide benefits in applications where there is a "high" flash point requirement. The by-
products can be used to supplement or replace conventional hazardous collectors for flotation
processes such as diesel fuel thereby reducing the dependency on such environmentally
unfriendly material. Diesel fuel is used ubiquitously in the mineral processing industry. A good
portion of the spent diesel from the processes is injected underground posing an environmental
and human health hazard, The present invention offers an added benefit of not posing any
environmental and/or human health hazard if discharged underground.
In at least one embodiment the glycerides and fatty acid mixtures are co-products
or by-products of an ethanoi process. They are considered green compositions because they are
non-hazardous and are derived from natural, renewable resources. These renewable resources
include corn.
Algae can be used to produce ethanoi. GFA can be derived from algae,
Ethanoi can be derived from corn utilizing a dry milling process, where the entire
corn kennel is ground into flour, and mixed with waiter. Enzymes are added to convert the starch
to sugar. Yeast is then added to convert the sugar to ethanoi. The solution, commonly referred
to as wash, meal, beer mash or sour mash, is then distilled separating the ethanoi from the
remaining portion or stillage, commonly referred to as me whole stillage, thick stillage, or thick
slop. The nonfermentable parts are separated. Trie solids are combined Into feed co-product
called distillers dried grain with solubles (DDGS). The liquid portion, which can contain some

solids, is referred to as the thin stillage, Glyceride and fatty acid mixtures can be extracted from
the thin stillage and/or the DOGS. The GFA can be referred to as "post fermentation corn oil".
US Published Patent Application 2009/0008301, discloses using hydrophobicity
enhancing reagents employing naturally occurring lipids and that triacylglycerols can be readily
hydrolyzed to fatty acids. Because vegetable oils are produced by solvent extraction; some of the
impurities in the crude oil, such as free fatty acids and phospholipids, are removed from crude
vegetable oils by alkali refining and precipitation. US Published Patent Application
2009/0008301 does not teach GFA generated from an ethanoi process.
The present invention differs from the commercial vegetable oils. The
commercial vegetable oils are refined, bleached and deodorized (RBD). Generally, RBD
commercial corn oil contains zero free fatty acids. As a result, the prior art teaches away any
intent to utilize the glycerides and fatty acid mixtures derived from an cthanol process.
US Patents 7,497,955 and 7,566,469 and US Patent Application 12/949850
disclose methods of dewatering thin stillage from an ethanoi process utilizing polymers. GFA
can be extracted from different phases of the ethanoi process. . Various methods are disclosed
for improving the capture efficiency of the oil from several streams of the ethanoi process such as
the dry milling process of making both food and fuel grade ethanoi from corn. 'In at least one
embodiment, in an ethanoi process, ethanoi is retrieved from the beer mash in a stripper column
and the remaining corn stillage solids are dewatered and a rich supply of glycerides and fatty acid
mixtures are recovered from the corn stillage solids.
In at least one embodiment, glycerides and fatty acid mixtures are derived as a by-
product from an ethanoi process. As described in a published article --" The Composition of
Crude Corn Oil Recovered after Fermentation via Csntrifugationfrom a Commercial Dry Grind
Ethanoi Process", Jonrnal of the Ameriean Oil Chemists Society; Vol. S7 pp. 895-902, by
Robert Moreau, Kevin Hicks, David Johnston,, and Nathan 'Laun, July 26, 2010, the composition

of these by-products are quite different from commercial corn oil and unrefined corn oil, and as a
result, the GFA marked effectiveness is unexpected. For example, the levels of free fatty acids in
the post fermentation corn oil are higher than in the RBI) oil or unrefined oil. The levels of free
sterols and hydroxycinnamate stery1 esters in the GFA are also higher than in commercial oil.
Levels of hydroxycinnamate steryl esters in the GFA ranged about 0.3 to 0.5 weight percent,
while levels of hydToxyeinnamate in commercial corn oil was non-detected. Moreover, the
earotenoids levels are much higher in the GFA at concentrations above 250 micrograms per gram
of GFA. In an embodiment, the carotenoids level is 250 micrograms per gram of GFA, or
greater.
Moreover, because of the exposure to all upstream processes of a fuel ethanol
plant, including high-temperature liquefaction, saccharifleation, and fermentation, the byproducts
have lowered levels of tocopherols. Tocopherols in commercial vegetable oil that is unrefined
were reported to be about 319 mg per 100 g of oil. Tocopherols in the present invention
averaged about 100 mg per 100 g of oil.
Recent federal ruling mandates that 15 billion gallons of com based ethanol are to
be used in commerce by 2022. EPA recognized extraction of the glycerides and fatty acid stream
from a fuel ethanol processes is beneficial in terms of ethanol process improvements and
lowering greenhouse gas emissions from a holistic ethanol life cycle perspective. One benefit is
utilizing the glycerides and fatty acid mixtures as & feedstock to make biodiesel. It is estimated
that 0.5 pound to i .4 pound of glycerides and fatty acid mixtures can be derived from a bushel of
corn used for ethanol production.
in at least one embodiment, the Invention provides methods of enhancing the
hydrophobicily of compounds in certain beneficiation processes. For example, the beneficiation
compositions comprising the glycerides and fatty acid mixtures can be useful in beneficiation of
the following materials including, but not limited to, the group of coal, plastics, sand and gravel,

phosphates, diamonds, and other mineral ores or man-made matter. In alternative embodiments,
the beneficiation compositions can be used in processes to increase the hydrophobicity of
particulate materials, particularly in applications such as flotation resulting in the beneficiation of
coal, phosphates, diamond ore, and the like. The beneficiation compositions can also be used in
conjunction with other suitable flotation collectors and promoters.
Flotation processes are one of the most widely used methods of separating the
valuable material from valueless material present, for example, in particulates or fines. For
example, in this process, the fine particles are dispersed In water or other suitable solution and
small air bubbles are introduced to the slurry so that hydrophobic particles can be selectively
collected on the surface of the air bubbles and exit the slurry (e.g. by rising to the surface) while
hydrophilic particles are left behind. The hydrophilic particles can also sink to the bottom of the
slurry to be collected as a sludge.
The glycerides and fatty acid mixtures can be used to separate materials, for
example, in any suitable flotation process. It should be appreciated that the desired final products
can rise to the surface during flotation and/or sink to the bottom, such as in reverse flotation
processes. For example, during silica notation processes, the desired product can sink to the
bottom of the slurry and the waste product can rise to the top of the slurry.
In at least one embodiment, the method includes separating a first material from a
second material. For example, the method can comprise mixing the first material and the second
material in a slurry wjth a beneficiation composition. The first material can be water; the second
materia! is being dewatered. The dewatering composition can comprise one or more glycerides
and fatty acid mixtures.
In at least one embodiment the glycerides and fatty acid mixtures is applied as an
emulsion. Emulsions of the glyceride and fatty acid mixtures can help to disperse the mixtures,

obtaining similar performance at less active concentration. The emulsion can contain an
emulsion stabilizing reagent.
The materials to be separated can have any suitable size. By example and in no
way limiting the inventive concept, the materials can range from 2 mm to 0.1 mm in size. The
slurry can also have up to 50% solids. Any suitable mechanical or chemical forces can be used
to bring the slurry particles in contact with the benefsciation compositions of the present
invention. The floated product and the non-floated tailings can be collected by any suitable
means currently known in the art.
EXAMPLES
The foregoing may be better understood by reference to the following
examples, which are presented for purposes of illustration end are not intended to limit
the scope of the invention.
EXAMPLE 1: A sample of coal slurry taken from a customer location was floated
in the laboratory using a Denver flotation machine. The tests were designed to determine
the utility of the glycerides and fatty acid mixtures as standalone collectors. The coal
feed slurry was fed into the flotation cell; consequently, separating into two streams the
concentrate and the tail. Three sets of samples were run. Five concentrate samples and
one tail samples were collected for each set. The % ash and % yield are listed in Table 1
for individual samples as well as for cumulative samples. The cumulative samples'
percent ash and percent yield combine the individual samples' percent ash and percent
yield. The ash represents the non-useable portion of the coal slurry; the concentrate or
percent yield contains the useable portion of the slurry. The glycerides and fatty acid
mixture was tested against diesel fual, a common collector, In some cases it is typical to
add a frother in the process to promote bubble formation enhancing the babble-particle

aggregates. In example 1, the frother used was a mixture of alcohols containing methyl
isobutyl earbinoi. The dosages of the collector and frother are listed in Table 1,
The % ash and the % yield were compared using diesel versus the
glycerides and fatty acid mixtures. The concentrate % yields were comparable for both
the diesel and the glycerides and fatty acid mixtures for all three sets of data. Similarly
the % ash matches closely using between the two collectors. The results indicate the
glycerides and fatty acid mixtures is as effective as diesel under the same conditions. The
average feed ash(%) was 43%.
Table 1. Comparison of Collector Performance of Diesel Fuel versus Glyceride
and Fatty acid mixtures (New Chemical as Collector).

EXAMPLES 2 AND 3: The flotation tests were conducted in a 1.5L Denver flotation
machine to demonstrate that GFA (glycerides and fatty actd mixture) can be applied for coal
flotation. Both hard-to-fioat and easy-to-float coal samples were used for the tests. GFA was

used as collector either in oi5y or in emulsions. The GFA emulsions were made with mechanical
agitation by adding emulsifiers (soy lecithin and Tween 81) and frother. Trie following
formulations are typical GFA emulsions:
Emulsion A: 36%GFA, 10% frother, 2% soy lecithin, 2% Tween 81 and 50% water
Emulsion B: 26%GFA, 10% #2 diesel, 10% frother, 2% soy lecithin, 2% Tween 81 and
50% water
Emulsion C: 46%GFA, 10% frother, 2% soy lecithin, 2% Tween 81 and 40% water
Emulsion D: 33%GFA, 13% #2 diesel, 10% frother, 2% soy lecithin, 2% Tween 81 and
40% water
In Examples 2 and 3, recovery data is listed. Recovery is defined as the percent of the valuable
mineral in the feed reporting into the concentrate.
Example 2: Shown in Table 2 are the results obtained with an easy-to-float coai slurry sample.
GFA and its emulsions were used as collectors under various dosages. Without collector, the
flotation recovery achieved 86%. This indicated that this coal is easy-to-float. With addition of
#2 diesel fuel, the maximum flotation recovery achieved was 88%. With addition of GFA and
emulsions A, B, C, D, the maximum flotation recovery reached 90-91%, These results implied
that GFA and its emulsions behaved stronger over #2 diesel as collector for easy-to-float coai.

Table 2. Flotation results with GFA and its emulsions as collectors for tlie easy-
to-float coal sample flotation. Frother dosage is 160g/t.

Example3: Shown in Table 3 are the results obtained with a hard-to-float coal slurry sample.
GFA and its emulsions were used as collectors under various dosages. Without collector, the
flotation recovery achieved only 13%. This indicated that this coal is hard-to-float. With addition
of #2 diesel fuel, the, maximum flotation recovery achieved was 70%. With addition of GFA and
emulsions B> C, D, the maximum flotation recovery reached 80%. These results implied that
GFA and its emulsions are more effective than #2 diese! as collector for hard-to-float coal.

Table 3. Flotation results with GFA and its emulsions as collectors for the hard-
to-float coal sample. Frother dosage is 300g/t.

While this invention may be embodied in many different forms 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 described herein and incorporated herein,
The above disclosure is intended to be illustrative and not exhaustive. This
description will suggest many variations and alternatives to one of ordinary skill in this art. All
these alternatives and variations are intended to be included within the scope of the claims where
the term "comprising" means "including, but not limited to". Those familiar with the art may
recognize other equivalents to the specific embodiments described herein which equivalents are
also intended to be encompassed by the claimsv-

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 slated
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; 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.
This completes the description of the preferred and alternate embodiments of the
invention. Those skilled in the art may recognize other equivalents to the specific embodiment
described herein which equivalents are intended to be encompassed by the claims attached
hereto.

We Claim:
1. A method of separating a first material from a second material, the method comprising
the steps of: mixing the first material and the second material in a slurry with a beneficiation
composition, providing air bubbles in the slurry to form bubble-particle aggregates with the first
material, and allowing the bubble-particle aggregates to be separated from the second material;
wherein the beneficiation composition comprises at least one glycerides and fatty acid mixtures
extracted from an ethanol process,
2. The method of Claim 1, wherein the glycerides and fatty acid rnixtures contain 5 percent
by weight of free fatty acids or greater.
3. The method of Claim 1, wherein the glycerides and fatty acid mixtures further comprise
one or more component selected from a list of linoleic acid, phytosterols, tocopherols,
hydroxycinnarnate steryl esters, lutein, -zeaxanthin, and carotenoids.
4. The method of Claim 2, wherein the glyceride and fatty acid mixtures is extracted from
the thin sttllage of a dry mill corn ethanol plant or from the distillers grains and solubles of a dry
mill corn ethanol plant.
5. The method of Claim 3, wherein the tocopherols' concentration is 150 mg per 100 g of
glycerides and fatty acid mixtures, or less. -
6. The method of Claim 3, wherein the carotenoids' concentration is 250 microgram per
grain of glycerides and fatty acid mixtures, or greater.
7. 7- The method of Claim 1, wherein the fatty glyceride and fatty acid mixtures is
applied as an emulsion.
8. The method of Claim 7, wherein the glycerides and fatty acid mixtures are combined with
one or more of collectors and frothers.

9. A method of dewatsring utilizing at least one glycerides and fatly acid mixtures extracted
from an ethanol process.
16, The method of Claim 9, wherein the glycerides and fatty acid mixtures further comprise
one or more component selected from a list of lenoleic acid, phytosierols, tocopherols,
hydroxycinnamatesteryl esters, lutein, - zeaxanthin, and carotenoids.
11. The method of Claim 9, wherein the glyceride and fatty acid mixtures is extracted from
the thin stillage of a dry mill com ethanol plant or from the distillers grains and solubles of a dry
mill com ethanol plant.
12. The method of Claim 10, wherein the tocopherols' concentration is 150 mg per 100 g of
glycerides and fatty acid mixtures, or iess.
13. The method of Claim 10, wherein the carotenoids' concentration
is 250 microgram per gram of glycerides and fatty acid mixtures, or more.