U.S. patent application number 15/856252 was filed with the patent office on 2018-05-03 for compositions of cosmetic, personal care and skin care products derived from lipid feedstocks and methods to produce the same.
This patent application is currently assigned to Valicor, Inc.. The applicant listed for this patent is Valicor, Inc.. Invention is credited to Jennifer L. Aurandt, James Robert Bleyer, Raymond Paul Roach.
Application Number | 20180116949 15/856252 |
Document ID | / |
Family ID | 53520391 |
Filed Date | 2018-05-03 |
United States Patent
Application |
20180116949 |
Kind Code |
A1 |
Bleyer; James Robert ; et
al. |
May 3, 2018 |
COMPOSITIONS OF COSMETIC, PERSONAL CARE AND SKIN CARE PRODUCTS
DERIVED FROM LIPID FEEDSTOCKS AND METHODS TO PRODUCE THE SAME
Abstract
Lipid compositions derived from a solvent-extracted distillers
oil of a dry grind ethanol process and lipid compositions included
in cosmetic products, personal care products, skin care products,
nutraceuticals, bio fuels, bio-lubricants, oleo chemicals,
nutritional products, other bio-products, and animal feed
compositions. Concentrations of lipid components.
Inventors: |
Bleyer; James Robert;
(Maumee, OH) ; Aurandt; Jennifer L.; (Brighton,
MI) ; Roach; Raymond Paul; (Midland, MI) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Valicor, Inc. |
Dexter |
MI |
US |
|
|
Assignee: |
Valicor, Inc.
Dexter
MI
|
Family ID: |
53520391 |
Appl. No.: |
15/856252 |
Filed: |
December 28, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14594572 |
Jan 12, 2015 |
9889084 |
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15856252 |
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61925934 |
Jan 10, 2014 |
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62062286 |
Oct 10, 2014 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C11B 3/10 20130101; C11B
3/14 20130101; A61Q 17/04 20130101; A61Q 5/12 20130101; A61K 8/361
20130101; A61Q 5/02 20130101; A23K 50/30 20160501; A23K 50/75
20160501; A61Q 3/02 20130101; C11C 3/003 20130101; Y02E 50/13
20130101; A23K 50/10 20160501; A61K 8/345 20130101; A61K 8/375
20130101; C11B 3/001 20130101; C07C 67/03 20130101; C10M 101/04
20130101; A23K 20/158 20160501; A23K 20/179 20160501; C10L 1/026
20130101; A23K 10/38 20160501; A61K 31/047 20130101; A61K 8/342
20130101; A61K 8/922 20130101; A61K 8/925 20130101; C11B 3/006
20130101; A61K 31/355 20130101; C11B 7/0075 20130101; A23D 9/007
20130101; A61K 2800/10 20130101; C10L 1/02 20130101; Y02P 60/873
20151101; A61K 8/678 20130101; Y02P 60/87 20151101; A23K 20/111
20160501; A61Q 19/00 20130101; Y02E 50/10 20130101; C07C 67/03
20130101; C07C 69/52 20130101 |
International
Class: |
A61K 8/92 20060101
A61K008/92; C11C 3/00 20060101 C11C003/00; C11B 7/00 20060101
C11B007/00; C11B 3/14 20060101 C11B003/14; C11B 3/10 20060101
C11B003/10; C11B 3/00 20060101 C11B003/00; C10M 101/04 20060101
C10M101/04; C10L 1/02 20060101 C10L001/02; C07C 67/03 20060101
C07C067/03; A61Q 19/00 20060101 A61Q019/00; A61K 31/355 20060101
A61K031/355; A61K 31/047 20060101 A61K031/047; A61K 8/67 20060101
A61K008/67; A61K 8/37 20060101 A61K008/37; A61K 8/36 20060101
A61K008/36; A61K 8/34 20060101 A61K008/34; A23D 9/007 20060101
A23D009/007 |
Claims
1. A lipid composition derived from a solvent-extracted distillers
oil of a dry grind ethanol process comprising: triglycerides
content not less than 96% w/w; free fatty acids content not greater
than 4% w/w; total moisture and insolubles content not greater than
1.5% w/w; total carotenoid content not greater than 50 ppm w/w; and
at least one component selected from the group consisting of total
lutein content not greater than 50 ppm w/w, cis-lutein/zeaxanthin
content not greater than 10 ppm w/w, .alpha.-cryptoxanthin content
not greater than 5 ppm w/w, .beta.-cryptoxanthin content not
greater than 5 ppm w/w, .alpha.-carotene content not greater than
0.5 ppm w/w, and cis-.beta.-carotene not greater than 0.1 ppm
w/w.
2. The lipid composition of claim 1, wherein said free fatty acid
content is not greater than 2% w/w and said triglycerides content
is not less than 98% w/w.
3. The lipid composition of claim 1, wherein said free fatty acid
content is not greater than 1% w/w and said triglycerides content
is not less than 98.5% w/w.
4. The lipid composition of claim 1, wherein said total carotenoid
content is not greater than 1 ppm w/w.
5. A composition derived from a solvent-extracted distillers oil of
a dry grind ethanol process comprising a concentration of a lipid
component wherein the concentration w/w of said lipid component is
at least twice a concentration of said lipid component in a lipid
feedstock, selected from the group consisting of free fatty acids,
.alpha.-tocopherol, total tocopherols, total carotenoids, lutein,
zeaxanthin, and total sterols.
6. A composition derived from a solvent-extracted distillers oil of
a dry-grind ethanol process comprising a concentration of a lipid
component wherein the concentration w/w of said lipid component is
one half or less of a concentration of said lipid component in said
distillers oil, said lipid component selected from the group
consisting of free fatty acids, .alpha.-tocopherol, total
tocopherols, total carotenoids, lutein, zeaxanthin, and total
sterols.
7. The lipid composition of claim 1, wherein said lipid composition
is included in a product chosen from the group consisting of
nutraceuticals, bio fuels, bio-lubricants, oleo chemicals,
nutritional products and other bio-products.
8. An animal feed composition comprising the lipid composition of
claim 1.
9. A cosmetic, personal care, or skin care product comprising the
lipid composition of claim 1.
10. The cosmetic, personal care, or skin care product of claim 9,
chosen from the group consisting of shampoos, hair lotions, skin
care products, skin lotions, skin protection products, sunscreen
lotion, self tanning products, nail creams, and nail polish.
11. Nutraceuticals, bio fuels, bio-lubricants, oleo chemicals,
nutritional products and other bio-products comprising the lipid
composition of claim 1.
12. An animal feed composition comprising the lipid composition of
claim 1.
13. A lipid composition comprising: free fatty acids of about 5%
w/w or less; and total carotenoids of about 500 ppm w/w or
greater.
14. A lipid composition comprising a phospholipid content greater
than that of a feedstock.
15. A lipid composition derived from solvent-extracted distillers
oil of a dry-grind ethanol process comprising a phospholipid
content greater than that of said distillers oil from which said
composition is derived.
Description
BACKGROUND OF THE INVENTION
1. Technical Field
[0001] The present invention relates to compositions comprising
lipids and beneficial lipid soluble non-glyceride compounds and
methods to produce such compositions. More specifically, the
present invention relates to compositions for use in cosmetic,
personal care and skin care applications and methods to produce
such compositions.
2. Background Art
[0002] The cosmetic, personal care, and skin care industry uses a
myriad of plant, vegetable, fruit, and seed oils in formulations
such as treatment creams, massage and bath products, skin
cleansing, and hair conditioning products.
[0003] These oils contain lipids; such as waxes, fatty acids,
sterols and lipid soluble components; such as tocopherols and
carotenoids, and have a variety of properties and
functionalities.
[0004] Coverage of the upper layer of the skin with natural oils
reduces trans-epidermal water loss (TEWL) and maintains water in
the upper layer of the skin contributing to enhanced hydration.
TEWL is a measure of barrier integrity and is defined as the
quantification of water that passes from inside the body through
the skin to the surrounding atmosphere via diffusion and
evaporation. The stronger the barrier, the lower the TEWL.
[0005] The fatty acids can be non-essential fatty acids; such as
oleic, palmitic, palmitoleic, lauric, and stearic acids or
essential fatty acids; such as linoleic and linolenic. Fatty acids
can be saturated (stearic, caprilic, palmitic) or unsaturated
(oleic, linoleic) and can exist in their free form or as glycerol
esters. They can be used in their anhydrous state or as an
oil/water emulsion. Fatty acids are used primarily as a skin
conditioner and as a carrier for other components.
[0006] Fatty acids are an important component of the skin's
intracellular lipid lamellae matrix and human sebum. Human sebum
includes more than 40% fatty acids; therefore, selected acids, when
applied, can partition into the sebum and the follicular opening.
Fatty acids are also part of the outer layer of the skin, the
stratum corneum. The skin's barrier properties are partially
dependent upon the unique organization of ceramides, sterols
(mostly cholesterol), and free fatty acids arranged as
extra-cellular lamellar bilayers between corneocytes.
[0007] Individual fatty acids have particular functionality with
respect to cosmetic and skin care applications. For example, oleic
acid has been shown to enhance skin permeation of various active
compounds. It is theorized that the mechanism of action attributed
for permeation enhancement is fluidization of the organized
lamellar organization in the stratum corneum. Linoleic acid is
known to play a role in maintaining an intact stratum corneum layer
and to elevate the rate of epidermal cell proliferation and
therefore skin renewal. Skin disorders such as eczema, psoriasis
and dermatitis have been related to deficiencies in linoleic acid.
Palmitoleic acid was found to exhibit anti-microbial activity
effective against gram positive bacteria, suggesting usefulness in
topical formulations for treatment of secondary gram positive
bacterial infections.
[0008] Fatty acids are also used as a carrier for other lipids and
lipid soluble compounds such as phytosterols, tocopherols,
tocotrienes, and carotenoids. These compounds absorb more
efficiently when combined with specific fatty acids. However,
topically applied esterified fatty acids such as triacylglycerols
must first be cleaved to their free acid form by lipase enzymes
present in eccrine/sebaceous secretions. Topically applied free
fatty acids can be absorbed directly. The kinetics of absorption of
topically applied lipids and lipid soluble compounds increase with
increasing ratios of free fatty acids to acyl glycerides.
[0009] Phytosterols are a naturally occurring plant sterol. It is
well known that phytosterols have anti-inflammatory properties and
are used in personal care products including anti-aging products.
The breakdown and loss of collagen is a contributing factor to the
aging of skin. Unprotected exposure to the sun accelerates this
aging phenomenon. According to a study by Germany's National
Institute of Health, topical treatments containing phytosterols are
effective in blocking the reduced collagen synthesis after UV
irradiation and have stimulatory effects. The study concluded
phytosterols "may be useful additions to anti-aging products".
[0010] Tocopherols and tocotrienes are valuable in skin care
applications for their anti-oxidant properties that protect against
DNA damage caused by environmental free radicals that promote
premature aging. .alpha.-Tocopherol is an antioxidant responsible
for quenching lipid peroxyl free radicals thereby protecting
against acute and chronic UV-induced damage. Collagen synthesis and
inhibition of collagen degradation was enhanced with tocopherol
application thereby preventing wrinkle formation and preserving
skin elasticity. In addition, tocopherols exhibit anti-inflammatory
activity by decreasing prostaglandin signaling.
[0011] Carotenoids are also incorporated into skin care products to
counteract premature aging caused by free radicals. Carotenoids are
naturally occurring plant pigments that protect plants against
excessive exposure to UV radiation and have been shown to provide
photoprotection to light exposed human tissue. The human skin, as
the boundary organ between the human body and the environment, is
under the constant influence of free radicals (FR), both from the
outside in and from the inside out. Carotenoids are known to be
powerful antioxidant substances playing an essential role in the
reactions of neutralization of FR (mainly reactive oxygen species
ROS). Carotenoid molecules present in the tissue are capable of
neutralizing FR, especially ROS, and are then destroyed. In a study
published in Skin Pharmacol Physiol, it was shown that this UV
protection is imparted with either oral ingestion or topical
application and an accretive effect was demonstrated with combined
oral ingestion and topical application.
[0012] In addition to their role in promoting skin health,
carotenoids also have applications in beauty products. These plant
pigments accumulate in the stratum corneum causing a yellow/red
coloring of the skin, giving a healthier and more attractive
appearance. As with the use of carotenoids for UV protection, the
benefit of using carotenoids for skin coloration occurs whether the
carotenoids are administered through oral ingestion or topical
application.
[0013] The cosmetic, personal care and skin care industry desires
natural and naturally derived products. Therefore there is a need
for a composition derived from a naturally occurring lipid
containing concentrations of compounds with desirable
functionalities and a method to produce such compositions.
[0014] The cosmetic industry places a high value on these
compositions. However, by-products and co-products are also created
and uses for these products must also be found to contribute to the
economic feasibility of the processes described herein. The
expanded use of the products of the present invention add to the
process economy of scale.
[0015] Rudolph Diesel developed the diesel engine in the 1890's.
Because of its high power, efficiency and reliability, the diesel
engine became the engine of choice for demanding applications.
Rudolph Diesel envisioned the use of lipids as the fuel for this
engine. However, the widespread discovery of petroleum oil made
petroleum based diesel fuel cheap and abundant and it quickly
became the fuel of choice for diesel engines.
[0016] Recent concern over the diminution of petroleum reserves and
the environmental effects of diesel fuel has led to the search for
alternative fuels for diesel engines. The products of the present
invention are highly desirable as alternative energy
feedstocks.
[0017] Environmental concerns are also driving the search for
alternatives for other oleo chemical products, such as bio
lubricants, foams, plastics, dielectric fluids, solvents, paints
and coatings.
[0018] There is also a desire to produce animal feed products.
Laying hens are fed lutein to give egg yolks a more desirable
color. Isolated palmitic acid added to the finishing diet of beef
cattle is known to improve marbling. The hog industry desires
specific saturated/unsaturated fats ratios to promote leaner pork
products.
[0019] Isolation and recovery of beneficial lipid-soluble
non-glyceride compounds from various bio-based feedstocks has been
practiced for many years. Fernandes and Cabral [Bioresource
Technology 98 (2007) 2335-2350] reviewed recovery methods for
phytosterols, with the most common methods involving recovery from
distillates obtained during the deodorization of crude vegetable
oils. Deodorizer distillates, especially of soy, corn, wheat germ
and tall oil are enriched in phytosterols and hence are preferred
feedstocks for recovering purified concentrates of these beneficial
compounds. The methods addressed by Fernandes and Cabral are
focused on obtaining phytosterol concentrates in excess of 50 wt %
and more typically greater than 80 wt %. Many of the common
recovery methods involve hydrolysis and saponification of esters
followed by distillation of the unsaponifiable compounds, including
phytosterols.
[0020] Rodrigues, et al. [Recent Patents on Engineering 1 (2007)
95-102] reviewed published methods for deacidification of vegetable
oils, i.e. removal of free fatty acids (FFAs). Traditional
deacidification approaches include chemical, physical and solvent
extraction methods. Newer approaches include biological removal of
FFAs by microorganisms and enzymatic esterification, supercritical
fluid extraction and membrane processing. Rodrigues, et al.
highlighted solvent extraction with short chain alcohols,
alcohol/water mixtures and other polar solvents as particularly
useful for deacidification of crude vegetable based oils; however,
the focus is on removal of FFAs with retention of tocopherols and
tocotrienols in the raffinate oil rather than isolation and
recovery of these beneficial non-glyceride compounds in the solvent
extract. In several cited examples, Rodrigues et al. show that
addition of water (up to 20% w/w) to an alcohol helps to reduce the
amount of neutral oil (triglycerides) lost to the solvent, yet the
solvent retains FFA removal power. A further consequence of
increasing water concentration in an alcohol/water solvent mixture
is that beneficial non-glyceride compounds such as tocopherols,
sterol ester and carotenoids partition to the raffinate phase. Thus
water concentration in an alcohol solvent can be used to tailor the
partitioning of glycerides and non-glycerides in the extract and
raffinate phases. Solvent extraction has been applied to many plant
based oils including canola, coconut, corn, cottonseed, olive,
palm, rape, rice bran, sesame seed and various nut oils.
[0021] The tremendous growth of the United States ethanol industry
over the past ten years has also resulted in the growth of ethanol
byproducts including distillers dry grain with solubles (DDGS) and
distillers oil (DO). Ethanol, DDGS and DO yields are currently
about 21, 17.7, and 0.5 pounds per bushel of corn respectively (1
bushel=56 pounds shelled corn at 15.5 wt % moisture). Technology
improvements are expected to increase DO yields to over 1 pound per
bushel. Most US dry grind ethanol plants have installed DO recovery
systems and hence a supply of almost 4 billion pounds of DO is
theoretically available in the nearly 13.3 billion gallon US
ethanol market.
[0022] Although corn is the predominant grain used for producing
ethanol in the United States, milo, barley, wheat and other grains
are also used. In the case of these other feedstocks, analogous
distillers oil can also be recovered. Distillers oil produced
primarily from corn fermentation is known as distillers corn oil
(DCO) but can contain oils of other grains if fermented in the same
facility. The term DO as applied herein refers generically to any
oil recovered from a grain fermentation process, including
corn.
[0023] In the conventional dry grind ethanol process, grain is
ground, slurried in water, cooked and treated with enzymes to
convert starch to sugars. Yeast then convert the sugars to ethanol
and carbon dioxide during fermentation resulting in an ethanol rich
"beer". Ethanol is removed from the beer by distillation resulting
in "whole stillage," an aqueous slurry of unfermented dissolved and
suspended corn solids. Whole stillage is separated with a decanting
centrifuge into distillers wet grains containing the bulk of the
suspended solids of whole stillage and thin stillage containing
dissolved solids, fine suspended solids, protein and oil. Up to one
half of the thin stillage is recycled to the cook step and the
balance is concentrated to "syrup" in multi-effect evaporators.
Distillers oil is typically obtained by centrifugation of partially
concentrated thin stillage but can be recovered at various parts of
the process. Syrup may be sold as is or mixed with distillers wet
grains and dried to produce DDGS.
[0024] Investigators have shown that DCO has a composition
distinctly different from crude germ oil or refined germ oil, i.e.
edible corn oil for human consumption (Moreau et al., J. Am. Oil
Chem. Soc. 2010, 87, 895-902; Winkler-Moser, Industrial Crops and
Products 2011, 33, 572-578). Moreau et al. showed that free fatty
acids in post fermentation corn oil (DCO) are 11-16% w/w, much
higher than crude ethanol extracted whole kernel oil having about
1% w/w FFA or commercial edible oil (corn germ oil, refined,
bleached and deodorized) having no measurable FFA. With respect to
beneficial non-glyceride compounds, the levels of free phytosterols
and hydroxycinnamate sterylesters in DCO were higher than those of
corn germ oil and were comparable to those of ethanol-extracted
corn kernel oil. The levels of tocopherols were lower in DCO than
in either corn germ oil or ethanol extracted corn kernel oil. The
levels of lutein and zeaxanthin in DCO were much higher than those
in corn germ oil and were comparable to those in ethanol-extracted
corn kernel oil. Thus DCO and other distillers oils offer valuable
depots of FFAs and beneficial non-glyceride compounds if a
cost-effective recovery process can be developed. The present
invention provides for compositions and cost effective methods of
obtaining valuable lipid compositions from distillers oil and other
natural lipid sources.
[0025] Distillers oil is primarily sold as an animal feed component
or as a feedstock for the production of fatty acid methyl esters
(biodiesel). As a biodiesel feedstock, distillers oil commands a
lower price than soybean oil due to distillers oil's relatively
high free fatty acid content (>10 wt %). Modern ethanol plants
continually strive to maximize the financial return on each bushel
of purchased grain. A high value oil composition produced from
distillers oil and enriched in beneficial lipid soluble
non-glyceride compounds offers the ethanol producer a further
opportunity to improve their financial return on grain.
[0026] U.S. Pat. No. 8,702,819 assigned to Poet Research Inc.
discloses a corn oil composition containing less than 5 wt % free
fatty acids and greater than threshold levels of specific
carotenoids, e.g. greater than 50 micrograms/g lutein. Poet further
discloses a method of obtaining the low FFA oil composition by
treating DCO with alkali. Alkali neutralizes (saponifies) the free
fatty acids making them much less oil soluble and de-emulsifies the
oil for improved oil/water phase separation. The Poet patent
emphasizes production of low FFA oil; however, the recovery of an
oil composition enriched in beneficial lipid soluble non-glyceride
compounds is not disclosed.
[0027] Therefore there is a need for efficient methods to produce
compositions derived from low cost naturally occurring lipids
containing concentrations of compounds with desirable
functionalities.
SUMMARY OF THE INVENTION
[0028] The present invention provides for a lipid composition
derived from a solvent-extracted distillers oil of a dry grind
ethanol process including triglycerides content not less than 96%
w/w, free fatty acids content not greater than 4% w/w, total
moisture and insolubles content not greater than 1.5% w/w, total
carotenoid content not greater than 50 ppm w/w, and at least one
component selected from the group consisting of total lutein
content not greater than 50 ppm w/w, cis-lutein/zeaxanthin
[0029] content not greater than 10 ppm w/w, .alpha.-cryptoxanthin
content not greater than 5 ppm w/w, .beta.-cryptoxanthin content
not greater than 5 ppm w/w, .alpha.-carotene content not greater
than 0.5 ppm w/w, and cis-.beta.-carotene not greater than 0.1 ppm
w/w.
[0030] The present invention provides for a composition derived
from a solvent-extracted distillers oil of a dry grind ethanol
process including a concentration of a lipid component wherein the
concentration w/w of the lipid component is at least twice a
concentration of the lipid component in a lipid feedstock, selected
from the group of free fatty acids, .alpha.-tocopherol, total
tocopherols, total carotenoids, lutein, zeaxanthin, and total
sterols.
[0031] The present invention provides for a composition derived
from a solvent-extracted distillers oil of a dry grind ethanol
process including a concentration of a lipid component wherein the
concentration w/w of the lipid component is one half or less of a
concentration of the lipid component in a lipid feedstock, selected
from the group of free fatty acids, .alpha.-tocopherol, total
tocopherols, total carotenoids, lutein, zeaxanthin, and total
sterols.
[0032] The present invention provides for a lipid composition
including a phospholipid content greater than that of a
feedstock.
[0033] The present invention also provides for a cosmetic, personal
care, or skin care product including the lipid compositions
above.
[0034] The present invention provides for nutraceuticals, bio
fuels, bio-lubricants, oleo chemicals, nutritional products and
other bio-products including the lipid compositions above.
[0035] The present invention provides for an animal feed
composition including the lipid compositions above.
DESCRIPTION OF THE DRAWINGS
[0036] Other advantages of the present invention are readily
appreciated as the same becomes better understood by reference to
the following detailed description when considered in connection
with the accompanying drawings wherein:
[0037] FIG. 1 is a flowchart of a first embodiment of the invention
in which a lipid feedstock is mixed with a solvent and allowed to
separate to produce a light phase and heavy phase of purified oil
and solvent is removed from the light phase to produce a
concentrate of beneficial non-glyceride compounds;
[0038] FIG. 2 is a flowchart of a second embodiment of the
invention in which the raffinate of FIG. 1 is extracted a second
time to improve extraction efficiency;
[0039] FIG. 3 is a flowchart of a third embodiment of the
invention, in which a countercurrent extraction process is utilized
to improve solvent efficiency;
[0040] FIG. 4 is a flowchart of a fourth embodiment of the
invention in which the non-glyceride concentrate of previous
figures is further concentrated by removal of free fatty acids via
saponification of acyl glycerides and free fatty acids with alkali
water to produce a soapstock and subsequent acidification of the
soapstock allows recovery of a concentrated free fatty acid stream
and a mixture of water, glycerol, salts and other impurities;
[0041] FIG. 5 is a flowchart of the method of the present invention
incorporated into a fatty acid alkyl ester production process;
and
[0042] FIG. 6 is a flowchart of the method of the present invention
incorporated into an ethanol production process.
DETAILED DESCRIPTION OF THE INVENTION
[0043] The present invention generally provides for compositions
recovered from a naturally occurring lipid. The compositions can
include lipids, lipid and lipid soluble compounds, and specific
combinations of lipids and lipid soluble compounds. The present
invention also provides for the use of the compositions in a
cosmetic, personal care or skin care product or as an additive to
such products. The present invention also provides for the use of
the compositions as a feedstock for bio-fuel, bio-chemical,
bio-product or oleo chemical processes. The present invention
further provides for a composition including one or more of the
following: triglycerides, diglycerides, free fatty acids,
phospholipids, tocopherols, tocotrienols, carotenoids, and sterols.
The present invention further provides for methods to produce
various concentrations of lipids, lipid and lipid soluble
compounds, and various concentrations of specific combinations of
lipids and lipid soluble compounds.
[0044] The terms "triglycerides" and "triacylglycerides" are used
synonymously herein and refer to lipids having a glycerin backbone
esterified to three fatty acid (acyl) side chains.
[0045] The term "acyl glyceride" as used herein refers to lipids
having a glycerin backbone esterified to either one
(monoglyceride), two (diglyceride) or three (triglyceride) fatty
acids (acyl) side chains.
[0046] For simplicity, free fatty acids, tocopherols, tocotrienols,
carotenoids, sterols, and other extracted compounds are herein
collectively and individually referred to as "extracted
compounds".
[0047] "Biofuel" as used herein refers to a fuel derived from
living matter, whether animal or plant, and preferably contains
lipids. The biofuel can be bioethanol, biodiesel or renewable
diesel.
[0048] "Bio-lubricant" as used herein refers to a substance derived
from organic matter, whether animal or plant, used to reduce
friction and wear.
[0049] "Bio-products" as used herein refers to a chemical or other
manufactured product whose primary feedstock is derived from living
matter, whether animal or plant.
[0050] "Nutraceuticals" as used herein refers to a compound or
group of compounds including biological derived compounds that
promotes health, increased metabolic function, or general well
being of an organism including human and or animals.
[0051] "Nutritional product" as used herein refers to a compound or
group of compounds that fulfills specific nutritional requirements
of an organism including human and or animals.
[0052] "Polar" as used herein refers to a compound that has
portions of negative and/or positive charges forming negative
and/or positive dipoles. While a polar compound does not carry a
net electric charge, the electrons are unequally shared between the
nuclei. Water is considered a polar compound in the present
invention.
[0053] "Extract" or "extract phase" as used herein refers to a
mixture containing solvent and all compounds solubilized within the
solvent in a liquid-liquid extraction process. The extract phase is
enriched in one or more solvent soluble compounds originally
present in the lipid feed stream treated in the extraction
process.
[0054] "Concentrate" as used herein refers to the extract or
extract phase following removal of the extraction solvent. The
solvent can be a mixture of solvents including water.
[0055] "Raffinate" or "raffinate phase" as used herein refers to
the solvent lean phase produced in a liquid-liquid extraction
process. The raffinate phase is partially depleted in one or more
components transferred into the solvent/extract phase.
[0056] "Beneficial non-glyceride compounds" (or "BNGs") refers to
any of a family of lipid soluble non-glyceride compounds including
carotenoids, tocopherols, tocotrienols, phytosterols and
phytostanols that are soluble in the glyceride lipid fraction of
plant based oils and are widely recognized as beneficial in
cosmetic, nutraceutical, animal and human nutrition applications.
All compounds belonging to these families are characterized by
chemical structures possessing one or more cyclic carbon rings and
aliphatic or isoprenoid side chains. BNGs containing hydroxyl
groups can be found in free and ester forms.
[0057] The naturally occurring lipid, herein referred to as "lipid
feedstock" can be any lipid produced by plants or animals
including, but not limited to, corn oil, soybean oil, coconut oil,
rapeseed oil, canola oil, jajoba oil, rhea butter, walnut oil, palm
oil, palm kernel oil, mustard seed oil, poppy seed oil, linseed
oil, hemp oil, rice oil, avocado oil, wheat oil, milo oil, almond
oil, apricot oil, borage oil, castor oil, coffee oil, macadamia nut
oil, olive oil, sunflower oil, safflower oil, sesame oil, tomato
oil, pumpkin oil, peanut oil, cottonseed oil, fish oil, and krill
oil. The naturally occurring lipid can be from algae, fungi, or
other microorganisms. Thus, in general, the lipid compositions of
the present invention can be derived from a seed, plant, vegetable,
or animal-based lipid. The lipid compositions can be derived from a
lipid byproduct of a fermentation process, such as an alcohol
fermentation process.
[0058] Mechanical pressing and extraction with various solvents are
used to recover lipids and lipid soluble compounds from oil seeds,
plant material, and microorganisms. These primary recovery
processes and resulting oil products are well known and are not
part of the present invention. However, it has been discovered for
the first time that secondary extractions of mechanically pressed
or primary extracted naturally occurring lipids can exploit
differences in solubility limits to create unique product
fractions. These unique product fractions have high functionality
and usefulness in cosmetics, personal care and skin care products,
such as, but not limited to, shampoos, hair lotions, skin lotions,
skin protection products, sunscreen lotion, self tanning products,
nail creams, and nail polish. These unique product fractions also
have high functionality and usefulness in nutraceuticals, bio
fuels, bio-lubricants, oleo chemicals, nutritional products, other
bio-products, and animal feed compositions. Any of the lipid
compositions described herein can be used in the above described
products.
[0059] Therefore, the present invention provides for a method of
performing secondary extractions and recovering a lipid
composition, including the steps of performing a first extraction
on a lipid feedstock, performing a second extraction on a lipid
feedstock, and exploiting differences in solubility limits to
create unique product fractions derived from naturally occurring
lipids.
[0060] There are various solvents that dissolve glycerides, lipids,
and BNG's found in lipid feedstocks. Each of these components has
unique solubility profile in the solvent. It has been discovered
that by exploiting the different solubility profiles, the extracted
compounds can be preferentially removed and recovered and unique
products can be produced.
[0061] A method of secondary extraction and recovery of lipids and
lipid soluble compounds is as follows. It should be understood that
description of various process steps in this particular method can
apply in the other methods described herein. A lipid feedstock is
mixed with a solvent in a ratio sufficient to dissolve the desired
extracted compounds. Preferably, the solvent added is a polar
solvent, such as, but not limited to, low molecular weight
aldehydes, ketones (such as acetone), acetates, esters, furans,
alcohols having typically fewer than 6 carbon chains such as
methanol, ethanol and propanols, diols, polyols, organic acids such
as formic, acetic and propionic acid, water, and combinations of
solvents. The solvent can be a mixture of a polar solvent
containing up to 25% w/w water. Additionally, polar solvents can
include amphipathic solvents. Non-polar solvents can also be used.
Hexane can be used and is non-polar. Propane can be used as the
solvent. Carbon dioxide and/or super critical carbon dioxide can be
used as a solvent. When the feedstock is mixed with a solvent at a
proper ratio, most of the extracted compounds dissolve in the
solvent, but only a portion of the glycerides dissolve in the
solvent, thereby concentrating the extracted compounds.
[0062] The lipid feedstock is mixed with the solvent using one of
various methods including, but not limited to agitated tank,
cavitation pump, static mixer or other suitable mechanisms.
[0063] At least some of the solvent and at least some of the
extracted compounds dissolved in the solvent, known as the extract
phase, are separated from the feedstock-solvent mixture by one of
various methods including, but not limited to, quiescent
decantation, centrifugation, or other suitable methods. All of the
solvent and all of the dissolved extracted compounds can also be
removed from the feedstock-solvent mixture.
[0064] The solvent can be removed from the extract phase resulting
in a non-glyceride concentrate or concentrate phase containing
extracted compounds and glycerides. Various methods known to those
skilled in the art can be used to remove the solvent including, but
not limited to, evaporation, distillation, pervaporation, inert
vapor stripping, anti-solvent extraction/washing, and combinations
thereof. In anti-solvent washing, the extract phase is mixed with
an antisolvent, for example water, such that the solvent dissolves
in the antisolvent. The extracts are removed from the antisolvent
mixture by methods including, but not limited to, quiescent
decantation or centrifugation. Examples of evaporative methods for
solvent removal include but are not limited to single stage and
multi-stage fractional distillation, wiped or falling film
evaporation, steam stripping, pervaporation, and combinations
thereof.
[0065] Various process variables, such as choice of solvent, mix
time, oil temperature, solvent temperature and solvent/feedstock
ratios can be changed to achieve the desired concentration of the
extracted compounds in the concentrate phase. Various process steps
can be performed in a batch or continuous contacting device, such
as the mixing and separating steps. A continuous contacting device
can operate counter-currently and contain multiple contacting
stages.
[0066] The material remaining after removal of the extract phase,
known as the heavy phase or raffinate phase, is then collected and
can be further processed and/or used for various processes and
products such as biofuels and bio-lubricants. The raffinate phase
can also be used in cosmetic, personal care and skin care products
as is or after further processing. Any residual solvent can be
removed from the raffinate phase by various evaporative methods
known to those skilled in the art including, but not limited to,
evaporation (thin film, falling film and wiped film evaporators),
distillation (single and multi-stage fractional distillation),
inert vapor stripping (such as steam or hot air), anti-solvent
extraction, membrane based pervaporation, and combinations thereof.
The evaporated solvent can be condensed and recovered. It should be
understood that any of the methods described herein can be
performed batch-wise or continuously.
[0067] In one embodiment of the invention, shown in FIG. 1, a lipid
feedstock (12) is mixed with a solvent (14) by any suitable means
(16). The mixture is allowed to quiescent decant (18). The
raffinate phase (20) is collected as the heavy phase. The extract
phase (22) is collected as the light phase. The solvent (14) is
evaporated (24) from the extract phase and then condensed and
recovered for reuse. The extracted compounds and a portion of the
glycerides are recovered as a non-glyceride concentrate or
concentrate (26). The raffinate can be considered to be purified
oil, rich in triacylglycerides.
[0068] Therefore, the present invention provides for a method of
removing and recovering a lipid composition by mixing a lipid
feedstock with a solvent, separating the mixture into a raffinate
phase and an extract phase containing beneficial non-glyceride
compounds, removing solvent from the extract phase and obtaining a
concentrate phase, and recovering a lipid composition from the
concentrate phase.
[0069] The concentrate phase can contain high levels of lutein,
zeaxanthin, and other carotenoids, tocopherols, tocotrienes,
phytosterols, and other sterols. These beneficial non-glyceride
compounds have utility in cosmetic applications. Sterols are used
for their anti-inflammatory properties. Tocopherols, tocotrienes,
and carotenoids are used as antioxidants. Carotenoids are also used
as photoprotectants against UV exposure. High concentrations of
these compounds are desirable in cosmetic and personal care
products because it lowers the required inclusion rate of the lipid
carrier and thereby lessens its dilutive effect. Therefore, in one
embodiment, the concentrate phase is used as or added to a cosmetic
or personal care product.
[0070] In one embodiment, a phase enriched in phospholipids can be
recovered as a middle phase or phospholipid phase (28).
Phospholipids consist of a diglyceride with a phosphate group
covalently bonded to a polar organic molecule such a choline.
Phospholipids are amphipathic in nature, as they have a polar
phosphate and non-polar acyl moieties. This characteristic causes
phospholipids present in distillers oil and other natural oils to
partition at the solvent-oil interface during extraction, where the
acyl groups non-covalently bond with the non-polar raffinate and
phosphate component interacts with the polar solvent. Therefore,
the present invention provides for a lipid composition including a
phospholipid content greater than that of a feedstock. The present
invention also provides for a method of producing this lipid
composition by recovering the lipid composition from an interfacial
layer of a lipid extraction process.
[0071] Phospholipids are a natural emulsifier and are used in
cosmetic products to make stable oil-in-water emulsions.
Phospholipids also support the barrier function of the skin and
enhance bio-absorption of associated compounds making them
desirable for use in cosmetic products. Therefore, in one
embodiment, the phospholipid-enriched phase is used as or added to
a cosmetic or personal care product.
[0072] In this embodiment of the present invention, the lipid
feedstock contains one or more of the following: free fatty acids,
diglycerides, triglycerides, tocopherols, tocotrienols,
carotenoids, sterols, and other lipid soluble compounds. After
mixing with solvent, some or all of the lipids and lipid soluble
compounds are recovered from the lipid feedstock/solvent mixture.
The solvent phase is preferentially enriched in free fatty acids,
diglycerides, tocopherols, tocotrienols, carotenoids, sterols, and
other lipid soluble compounds. Beneficial non-glyceride compounds
(tocopherols, tocotrienols, sterols, fatty acids, carotenoids free
fatty acids, .alpha.-tocopherol, total tocopherols, total
carotenoids, lutein, zeaxanthin, and total sterols) can be
concentrated from the lipid composition. This concentrating can be
achieved by removing FFAs or glycerides by a method such as
shortpath or molecular distillation, saponification and phase
separation, chemical or enzymatic hydrolysis of glycerides,
liquid-liquid extraction, winterization, esterification,
trans-esterification, membranes, chromatography, and combinations
thereof. The present invention provides for a lipid composition
produced by this method.
[0073] The concentration of triglycerides is enriched in the
raffinate phase with a concomitant reduction of free fatty acids,
diglycerides, tocopherols, tocotrienols, carotenoids, sterols, and
other lipid soluble compounds. Solvent is removed from one or more
of the recovered phases including the raffinate phase and the
extract phase.
[0074] Triglycerides are often used as a carrier for lipid soluble
components in cosmetic and personal care products. High purity
triglycerides are desirable for such applications. Therefore, in
one embodiment, the raffinate phase is used as or an additive to a
cosmetic or personal care product.
[0075] In another embodiment of the invention, shown in FIG. 2, a
lipid feedstock is processed as in FIG. 1 (10) to produce a
raffinate (20). The raffinate phase is mixed (30) with a second
charge of solvent (14). The second solvent can be the same as the
first solvent or a different solvent. The mixture is allowed to
quiescent decant (32) into a second raffinate phase (34) and second
extract phase (36). The second extract phase is collected as the
light phase. The solvent (14) is evaporated from the second extract
phase and recovered for reuse and a second concentrate phase (38)
is recovered. The second concentrate phase can be optionally
combined with the first concentrate.
[0076] Therefore, the present invention provides for a method of
removing and recovering a lipid composition by mixing a lipid
feedstock with a solvent, separating the mixture into a raffinate
phase and an extract phase, removing solvent from the extract phase
and obtaining a first concentrate phase, mixing the raffinate phase
with a second solvent, separating the mixture into a second
raffinate phase and a second extract phase, removing the second
solvent from the second extract phase and obtaining a second
concentrate phase, and recovering a lipid composition from the
first and second concentrate phases. The present invention also
provides for a lipid composition recovered by this method.
[0077] Those skilled in the art will appreciate that the amount of
solvent required for the extraction process can be lessened by the
use of countercurrent wash steps. In a stage of the countercurrent
wash system, lipids are mixed with solvent then allowed to
quiescent decant. The light phase which contains the extract phase
is moved to the stage upstream. The heavy phase which contains the
raffinate phase is moved to the stage downstream.
[0078] Thus, in another embodiment of the invention, shown in FIG.
3, the lipid feedstock (12) is mixed with the solvent in a series
of countercurrent wash steps (40) until the raffinate phase or the
extract phase meets the desired specifications. The extract phase
(42) is collected as the light phase. The raffinate phase (44) is
collected as the heavy phase. In another embodiment, the solvent
can be evaporated and recovered for reuse and the concentrate phase
can be recovered.
[0079] The countercurrent wash steps can be further optimized
through the use of various liquid to liquid extraction columns
which are well known to those skilled in the art and incorporate
numerous mix zones and decantation zones. Examples of continuous
extraction columns are those offered by Sulzer Chemtech Ltd.
including "Kuhni" agitated columns, packed columns, and
mixer-settler columns.
[0080] The concentrate phase can be further processed to isolate
the various extracted compounds. The concentrate phase can be
subjected to saponification by adding alkali at various molar
ratios. At high levels of alkali to concentrate ratios, some or all
of the glycerides convert to free fatty acids and then some or all
of the free fatty acids convert to soaps. The soaps are water
soluble and can be removed by water washing the concentrate and
separating by various methods, including, but not limited to
quiescent decantation and centrifugation. The saponification
process is reversible. The soaps can be converted back to free
fatty acids by adding an acid to the soap solution. The free fatty
acids are not soluble in water and can be recovered by various
methods, including, but not limited to, quiescent decantation or
centrifugation. At low levels of alkali to concentrate ratios,
little or no glycerides are converted to free fatty acids; however,
the free fatty acids present in the concentrate convert to soaps.
The free fatty acids can be recovered using the process detailed
above.
[0081] The presence of phospholipids interferes with the
saponification process by acting as an emulsifier. In conventional
vegetable crude oil refining, phospholipids, also known as
phosphatides, are first removed by degumming (A. J. Dykstra,
Degumming--Introduction, AOCS Lipid Library). In the degumming
process, water or acidic water is mixed with the oil to solubilize
hydratable phosphatides. The free fatty acids of degummed oil can
then be processed by caustic refining, a saponification process.
Thus, in an embodiment of the present invention, the concentrate
phase can be degummed prior to saponification.
[0082] In another embodiment of the invention, shown in FIG. 4, a
lipid feedstock is processed as in FIG. 1 (10); the concentrate
phase (26) is mixed (46) with an alkali water solution (48) and
then separated by decantation (50). The light phase is collected as
a further concentrated Concentrate. The soap phase (54) is
collected as the heavy phase and contains soaps, water and
glycerol. Acid (56) is added to the soap phase, mixed (58) and then
decanted (60). Free fatty acids (62) are removed as the light phase
of the acid mixture. The heavy phase contains water, glycerol,
salts and other impurities (64).
[0083] In another embodiment, the water, glycerol, salts and other
impurities can be further separated. In another embodiment, the
glycerol can be further processed to increase purity.
[0084] Glycerol is used by the cosmetic and personal care industry
as a humectant, i.e. a substance that promotes the retention of
water. Therefore, the glycerol recovered by the present invention
can be used as or an additive to a cosmetic or personal care
product.
[0085] The raffinate phase can be processed into alcohol esters
with various methods including transesterification. The raffinate
phase can also be reacted with hydrogen and products of this
reaction can be recovered and separated from the reacted oil.
[0086] Therefore, another embodiment of the present invention
further includes mixing the raffinate phase with an alcohol and a
transesterification catalyst to produce alcohol esters and
glycerol. The present invention provides for the alcohol esters and
glycerol produced by these methods. Another embodiment of the
present invention includes reacting the raffinate phase with
hydrogen to produce one or more of the following: alkynes, naphtha,
and other hydrocarbons. The present invention provides for the
alkynes, naphtha, and other hydrocarbons produced by these
methods.
[0087] As a result of the process described above, some of the
triglycerides dissolve in the solvent and can be recovered with the
extracted compounds. The triglycerides can act as a carrier as an
effective method to deliver the cosmetic, personal care or skin
care product. Therefore, the value of the triglycerides can be
realized in the marketing of the extracts.
[0088] However, other cosmetic, personal care or skin care products
would consider high levels of triglycerides or certain fatty acids,
free fatty acids and/or some of the extracted compounds or other
components as deleterious or undesirable. Various methods can be
used to further concentrate the extracted compounds and/or remove
unwanted components.
[0089] Prior to mixing with solvents, the lipid feedstock can be
vacuum distilled to remove water and/or free fatty acids. Oil is
heated and held under vacuum such that water and/or free fatty
acids are volatilized. The water and/or free fatty acids can be
removed, condensed, and collected. Separation of free fatty acids
from deodorizer distillates by molecular (short path) distillation
has been described by Martins et al. (Separation and Purification
Technology, 2006, 48, 78-84).
[0090] Distillation can also be used to recover specific fatty
acids based on relative volatility and boiling points. Oil is
heated to the boiling point of the desired fatty acid. Fractional
distillation can be used to recovery multiple fatty acid streams.
Distillation can be performed at a pressure less than atmospheric
to reduce the required temperature. The feedstock for the process
can be any of the products of the current invention. Various
methods may be employed to increase the free fatty acid content
prior to distillation.
[0091] Prior to mixing with solvents, the lipid feedstock can
undergo winterization. In the winterization process, the feedstock
is chilled to precipitate compounds with high melting points such
as saturated fatty acids. Various solvents can be added to the
feedstock prior to winterization. The precipitated compounds can be
removed by various methods, including, but not limited to quiescent
decantation, centrifugation, or filtering. The feedstock for
winterization can be the lipid feedstock, the raffinate phase, the
extracted phase or the concentrate phase.
[0092] A lipid feedstock containing high melting point components
can be undesirable. For example, high levels of palmitic acid will
cause a lipid feedstock to solidify at room temperature. If a
cosmetic or personal care product is to remain liquefied at room
temperature, the palmitic acid must be removed from the lipid
feedstock. If a cosmetic or personal care product is to be
solidified at room temperature, palmitic acid can be added to lipid
feedstock.
[0093] Prior to mixing with the solvent, the lipid feedstock can
undergo degumming, deodorization, winterization, bleaching, or
combinations thereof.
[0094] One embodiment of the present invention includes subjecting
a feedstock to one or more of the following processes:
winterization, vacuum distillation, degumming, bleaching, or
deodorizing. Another embodiment of the present invention further
includes wherein the feedstock is one of lipid feedstock, raffinate
phase, extractable phase, or concentrate phase.
[0095] Any residual color can also be removed, such as from the low
FFA raffinate oil, by bleaching. Bleaching with, for example,
bleaching clay removes color bodies such as carotenoids. For
example, the raffinate oil can contain less than about 1 ppm total
carotenoids.
[0096] Residual color can be undesirable when using triglycerides
as a carrier for certain lipid soluble components. Therefore, in
one embodiment, raffinate oil with less than about 1 ppm
carotenoids is used as or an additive to a cosmetic or personal
care product.
[0097] Winterization of the lipid feedstock containing glycerides
is only marginally effective because the glycerides can be composed
of different fatty acids, thereby having different melting points
than the individual fatty acids that make up the glyceride. The
melting points of free fatty acids are dependent on their chain
length and degree of saturation. To improve on this process, the
glycerides can be converted to free fatty acids prior to
winterization. Various methods can be used including, but not
limited to, acid hydrolysis, enzymatic hydrolysis, caustic
hydrolysis, or any other suitable method. After winterization, the
free fatty acids can be converted back to glycerides.
[0098] Therefore, one embodiment of the present invention includes
converting some or all of glycerides in a feedstock to free fatty
acids. Another embodiment of the present invention further includes
cooling the feedstock to a temperature sufficient to precipitate
one or more of the free fatty acids. Another embodiment of the
present invention further includes cooling the feedstock to
selective temperatures to preferentially precipitate various free
fatty acids. Another embodiment of the present invention includes
recovering the various free fatty acids and glycerol. The present
invention provides for the free fatty acids and glycerol recovered
by these methods. Another embodiment of the present invention
comprises converting some or all of the free fatty acids to
glycerides. More specifically, prior to mixing, all or a portion of
triacylglycerides in the lipid feedstock can be converted to free
fatty acids by at least one process such as thermal hydrolysis,
hydrothermal hydrolysis, acid hydrolysis, base hydrolysis enzymatic
hydrolysis, and combinations thereof. Also prior to mixing, a
portion of the free fatty acids arising from triacylglyceride
hydrolysis can be removed by at least one process such as shortpath
or molecular distillation, saponification and phase separation,
winterization, and combinations thereof.
[0099] Winterization can also be effective on fatty acids
esterified with an alcohol. Any suitable process can be used to
esterify the fatty acids including, but not limited to, acid
esterification and transesterification. Enzymes can be used as a
catalyst for the esterification processes.
[0100] The free fatty acids can be removed from any of the phases
by mixing the phase with a caustic solution in a process known as
saponification. The free fatty acids form a soap that is water
soluble and can be removed by washing with water. The free fatty
acids can be recovered by neutralizing the water/soap mixture with
an acid, reversing the saponification reaction, converting the
soaps to free fatty acids. The free fatty acids can be removed and
recovered from the water.
[0101] The free fatty acids can be separated through various forms
of chromatography including, but not limited to, ion exchange,
size-exclusion, reverse phase, and two-dimensional. In certain
circumstances, individual fatty acids are desirable and can be
isolated using different forms of chromatography. In other
circumstances a combination of fatty acids are desirable.
[0102] Therefore, one embodiment of the present invention provides
for free fatty acids and methods to recover them. Free fatty acids
have utility in cosmetic and personal care products. Free fatty
acids are absorbed by the skin more readily than triglycerides.
Individual free fatty acids are used for a variety of purposes. As
described above oleic acid, linoleic acid, and palmitoleic acid are
examples of individual free fatty acids that have specific
functionalities. Therefore, in one embodiment, free fatty acids are
used as or additive to a cosmetic or personal care product.
[0103] Any of the phases can be saponified, transesterified, and
then optionally winterized. For example, the concentrate phase can
be mixed with a caustic solution to convert the free fatty acids to
soaps. Water can be added to the solution to dissolve the soaps.
The water and soaps can be removed by quiescent decantation. The
remaining concentrate phase can be recovered, dehydrated, heated,
and mixed with any suitable alcohol such as methanol and any
suitable catalyst such as sodium methylate causing the glycerides
to be converted to alcohol esters and glycerin. The glycerin can be
removed by quiescent decantation. Any suitable acid such as
hydrochloric acid may be added to aid in the removal of glycerin
and the recovery of the alcohol esters. The alcohol esters can be
washed with water and dehydrated. The extracted compounds will
remain with the alcohol esters throughout the process. The alcohol
esters can then be winterized using the process described
above.
[0104] The esterification process is reversible. The alcohol esters
can be heated and mixed with glycerin to convert the alcohol esters
to glycerides.
[0105] All or a portion of the raffinate phase, the extract phase
or the concentrate phase can undergo any one or combination of
winterization, esterification, saponification, or vacuum
distillation to provide a unique composition. Therefore, one
embodiment of the present invention includes subjecting a feedstock
to one or more of the following processes: winterization,
esterification, saponification, and vacuum distillation. The
feedstock can be one or more of the following: lipid feedstock,
raffinate phase, extract phase, and concentrate phase.
[0106] The fatty acids present in the raffinate, extract, or
concentrate phase can be saturated or unsaturated. Saturated fatty
acids can be more desirable than unsaturated fatty acids in certain
applications. Unsaturated fatty acids can be converted to saturated
fatty acids by various methods. In one method, a feedstock
containing unsaturated fatty acids is mixed with an appropriate
enzyme to convert the unsaturated fatty acids into saturated fatty
acids. In another method, a feedstock containing unsaturated fatty
acids is reacted with an appropriate catalyst to reduce the
carbon-carbon double bond. The feedstock can be the lipid
feedstock, the raffinate phase, the extract phase, or the
concentrate phase.
[0107] One embodiment of the present invention includes converting
glycerides to free fatty acids using any suitable method. Another
embodiment of the present invention further includes winterizing to
selectively recover various saturated fatty acids. Another
embodiment of the present invention further includes processing to
convert the unsaturated fatty acids to saturated fatty acids.
Another embodiment of the present invention further includes
converting the unsaturated fatty acids to saturated fatty acids and
winterizing to selectively recover various converted saturated
fatty acids. In one embodiment of the present invention, the
glycerides are contained in one or more of the following: lipid
feedstock, raffinate phase, extract phase, or concentrate phase.
Another embodiment of the present invention includes one or more of
the following: free fatty acids, saturated fatty acids, or
unsaturated fatty acids.
[0108] One embodiment of the invention includes separating one of
more of the following: lipid feedstock, raffinate phase, extract
phase, or concentrate phase by various forms of chromatography
including, but not limited to, ion exchange, size-exclusion,
reverse phase, and two dimensional. In certain circumstances
individual components are desirable and can be isolated using
different forms of chromatography. In other circumstances, a
combination of components is desirable. Therefore, one embodiment
of the present invention includes isolating one or more individual
components from one of more of the following: lipid feedstock,
raffinate phase, extract phase, concentrate phase.
[0109] The products, co-products and by-products produced can also
be used in or as a feedstock for nutraceuticals, bio fuels,
bio-lubricants, oleo chemicals, nutritional products, and other
bio-products.
[0110] The present invention also provides for a method of
purifying biofuel feedstock by removing color compounds, free fatty
acids, and waxes from a biofuel feedstock, and recovering a
purified biofuel. Each of the extract compounds can be removed as
well as recovered if desired as described above. By removing these
extracts, the biofuel that is produced is more pure than previous
biofuels.
[0111] Biodiesel producers prefer lipid feedstocks having low
levels of free fatty acids (typically less than 2% w/w and more
preferably less than 1% w/w) as free fatty acids neutralize and
therefore deactivate basic catalysts such as sodium methoxylate
used in the transesterification step. In order to accommodate
higher levels of free fatty acids biodiesel producers can deploy a
two-stage esterification process in which free fatty acids are
first converted to alkyl esters with an acid catalyst in a first
stage followed by a conventional base catalyzed second stage
transesterification. The two-catalyst process is not desirable as
it adds capital cost, operating cost, and process complexity. The
present invention provides for a biodiesel feedstock low in free
fatty acids, thus allowing the biodiesel producer to avoid the cost
and complexity of a two catalyst process.
[0112] FIG. 5 shows a method of producing alkyl esters with a
process of the present invention. A lipid feedstock is processed as
in FIG. 1 (10) to produce a raffinate (20). An alcohol (66) such as
methanol or ethanol and a catalyst (68) is mixed (70) with the
raffinate. The transesterification process is reversible so an
amount of alcohol above the stoichiometric requirements must be
added to drive the reaction toward the creation of alkyl esters.
The mixture is decanted (72) and the alkyl esters and excess
alcohol (74) are collected as the light phase. Glycerol (76) is
collected as the heavy phase. The alcohol (66) is separated from
the alkyl esters (78) by, for example, evaporation (80). The
alcohol can be recycled and used as the solvent in the extraction
process (10).
[0113] Thus, in one embodiment of the present invention free fatty
acids and beneficial non-glyceride compounds are removed from lipid
feedstock by extraction with a solvent. The raffinate phase is
purified oil preferably containing less than about 4% w/w FFA and
greater than 96% w/w triacylglycerides. More preferably the
raffinate phase contains less than 2% w/w FFA and greater than 98%
w/w triacylglycerides. Most preferably the raffinate phase contains
less than 1% w/w FFA and greater than 98.5% w/w triacylglycerides.
The purified raffinate phase is transesterified with an alcohol to
produce an alkyl ester. In one embodiment, the alcohol can be the
same alcohol used in the extraction process or in another
embodiment, a different alcohol can be chosen for
transesterification. Any suitable basic catalyst such as liquid
soluble sodium methylate or a solid phase catalyst can be used to
convert the glycerides to alkyl esters and glycerin. The glycerin
can be removed by quiescent decantation. Any suitable acid such as
hydrochloric acid may be added to aid in the removal of glycerin
and the recovery of the alkyl esters. The alkyl esters can be
washed with water and dehydrated. In another embodiment the alkyl
ester is used as a biofuel.
[0114] More specifically, the present invention provides for a
method of producing a fatty acid alkyl ester by extracting a lipid
feedstock with an alcohol to produce an extract phase and a low
free fatty acid (FFA) raffinate phase, reacting the low FFA
raffinate with alcohol to produce a fatty acid alkyl ester,
recovering excess alcohol from the reacting step, and recycling
recovered alcohol to the extraction step. The recovered alcohol can
be dehydrated prior to recycling to the extracting step.
[0115] The process of the present invention can also be physically
integrated or proximally located with a fatty acid alkyl ester or
biodiesel production facility. The lipid feedstock can be raw
materials, products, co-products, by-products, or intermediates of
the fatty acid alkyl ester or biodiesel facility. The solvent can
be an alcohol or an alcohol/water composition and can be a raw
material, co-product, by-product, and intermediate of the fatty
acid alkyl ester or biodiesel facility. The alcohol or
alcohol/water composition can be recycled to the integrated or
proximately located fatty acid alkyl ester or biodiesel facility
after it is used in the production of the oil compositions.
[0116] The raffinate can be bleached or winterized prior to
transesterification. Any residual solvent in the raffinate phase
can be used for the transesterification process. The recovered
solvent from the extraction process can be mixed with the recovered
solvent from biodiesel process for further dehydration.
[0117] Recently, bio-lubricants have commanded a larger percentage
of the lubricant market at the expense of petroleum based
lubricants. They are found in areas where contamination from
petroleum products is of concern such as in food production and
preparation equipment. Other uses include areas where total loss of
the product to the environment is expected to occur such as use in
marine equipment, agricultural equipment, chainsaws, transformers,
and transmission lines.
[0118] Bio-products are replacing traditional products in many
areas, especially where there is heightened environmental
awareness. The list of bio-based products is long and continually
expanding but a few examples include degradable plastics, paints,
solvents construction materials, carpet, and textiles.
[0119] The raffinate, extracted phase, and concentrate phase can be
processed to produce desired compositions of components by various
methods of the present invention. The compositions can be used in
cosmetic, personal care, and skin care products. The compositions
can be used in or as a feed stock for nutraceuticals, bio fuels,
bio-lubricants, oleo chemicals, nutritional products and other
bio-products.
[0120] Therefore, one embodiment of the present invention provides
for a composition including at least one of the following: free
fatty acids of about 15% w/w or greater, triglycerides of about 75%
w/w or less, and at least one further beneficial non-glyceride
compound including .alpha.-tocopherols of about 50 ppm w/w or
greater, total tocopherols of about 2000 ppm w/w or greater, total
carotenoids of about 300 ppm w/w or greater, lutein of about 100
ppm w/w or greater, zeaxanthin of about 100 ppm w/w or greater, and
levels of total sterols of about 2000 ppm w/w or greater.
[0121] In one embodiment, the present invention provides for a
lipid composition including at least one of the following: free
fatty acids of 4% w/w or less, total carotenoids of about 100 ppm
w/w or less, and triglycerides of greater than 96% w/w. More
preferably, the lipid composition includes a triglycerides content
not less than 96% w/w, free fatty acids content not greater than 4%
w/w, total moisture and insolubles content not greater than 1.5%
w/w, total carotenoid content not greater than 50 ppm w/w, and at
least one component selected from total lutein content not greater
than 50 ppm w/w, cis-lutein/zeaxanthin content not greater than 10
ppm w/w, .alpha.-cryptoxanthin content not greater than 5 ppm w/w,
.beta.-cryptoxanthin content not greater than 5 ppm w/w,
.alpha.-carotene content not greater than 0.5 ppm w/w, and
cis-.beta.-carotene not greater than 0.1 ppm w/w. In a more
preferred embodiment of the lipid composition, the free fatty acid
content is 2% w/w or less and triglycerides are greater than 98%
w/w. In a most preferred embodiment of the lipid composition, the
free fatty acid content is 1% w/w or less and triglycerides are
greater than 98.5% w/w. Also, more preferably, the total carotenoid
content is not greater than 1 ppm w/w.
[0122] In one embodiment, the present invention provides for a
lipid composition including: free fatty acids of about 5% w/w or
less and total carotenoids of about 500 ppm w/w or greater.
[0123] In one embodiment, the present invention provides for a
composition including a concentration of a lipid component selected
from the following wherein the concentration w/w of the lipid
component is at least twice the concentration of the lipid
component in the lipid feedstock: free fatty acids,
.alpha.-tocopherols, total tocopherols, total carotenoids, lutein,
zeaxanthin, and total sterols.
[0124] In one embodiment, the present invention provides for a
composition including a concentration of a lipid component selected
from the following wherein the concentration w/w of the lipid
component is one half or less of the concentration of the lipid
component in the lipid feedstock: free fatty acids,
.alpha.-tocopherols, total tocopherols, total carotenoids, lutein,
zeaxanthin, and total sterols.
[0125] In one embodiment of the present invention, the compositions
are derived from a lipid. The lipid can be naturally occurring. In
one embodiment of the present invention, the naturally occurring
lipid can be sourced as a co-product or by-product of agriculture,
feed, food, or fuel processes, including, but not limited to, a
grain ethanol plant. The grain ethanol plant can process one or
more of the following: corn, milo, wheat, or barley. In another
embodiment, the present invention provides for a composition
wherein such composition is isolated from one or more of the
following: corn oil and oil recovered from a fermentation process.
In another embodiment of the present invention, the oil can be
recovered from a fermentation process after at least one product of
fermentation has been removed from said process.
[0126] The process can be further economized by co-locating with
other processes, such as alcohol or biodiesel production. Such
co-location reduces capital and operating expense.
[0127] The co-location of the process with alcohol production, such
as ethanol, allows for several synergistic operations. In an
ethanol production process grain is milled, slurried and treated
with enzymes to release sugars. The sugars are fermented in a
fermenter. The resultant product is referred to as "beer". The
ethanol form the beer is removed by a beer column producing
rectifier feed. The rectifier removes more water from the ethanol.
The product is sent to a dehydration unit, such as a molecular
sieve to produce high proof ethanol. The residual product from the
beer column is referred to as "whole stillage." Whole stillage can
be centrifuged into wet cake and thin stillage. The wet cake can be
dried to produce dried distiller's grain. Some of the thin stillage
can be concentrated and added to either the wet cake or dried
distiller's grain. Distillers oil can be recovered at various
points in the process, such as from the grain slurry, whole
stillage, or thin stillage. Ethanol can be used as the solvent in
the extraction process and can be obtained from various points.
Ethanol can be obtained after the beer column, where the ethanol
concentration is typically around 50% w/w; from the rectifying
column, where the ethanol concentration is typically 95% w/w; or
from the molecular sieve or other dehydration unit, where the
concentration is typically over 98% w/w.
[0128] During the extraction process the ethanol can pick up
moisture. This wet ethanol can be returned to the ethanol process
for dehydration. The wet ethanol can be returned to one or more of
the following points in the process: the fermenter, the beer well,
the rectifier feed, dehydration unit feed, or any other suitable
place.
[0129] Any of the compositions and products of the present
invention can be added to co-products of the ethanol process, such
as the wet cake, distillers solubles (syrup), dried distillers
grain (DDG), high protein meal, or dried distillers grain with
solubles (DDGS). For example, the raffinate or phospholipid phase
can be added to the dried distiller's grain to increase its fat
level. Any of the lipid compositions can be removed from a lipid
feedstock and added to a distillers grain co-product. The lipid
feedstock can be distillers oil such as distillers corn oil.
[0130] Various methods can be used to extract other co-products
from the ethanol process that are suitable for adding products of
the present invention. For example, Bleyer, et al. in US
application 2014/0343259 A1, describe a method for extracting a
high protein meal. The high protein meal form this process or other
suitable process can be added to the extracted phase or extracted
phase concentrate to produce a high protein, high carotenoid animal
feed product.
[0131] FIG. 6 depicts the integration of a lipid extraction process
with a alcohol production facility. Grain is milled (84), slurried
(86) and fermented into an alcohol to produce a beer. The beer is
distilled (90) and alcohol and whole stillage are recovered. The
whole stillage is separated (92) into stillage and wet cake. The
stillage is separated (94) into a lipid feedstock and a de-oiled
stillage. Alternatively, a lipid feedstock can be recovered prior
to fermentation, e.g. from the grain slurry (86). A high protein
meal can be extracted (96) from the de-oiled stillage. The balance
of the de-oiled stillage can be mixed (98) with the wet cake to
produce DDGS. The concentrate (26) resulting from the extraction
(10) can be mixed (100) with the protein meal to produce a high
protein meal enriched with carotenoids. The phospholipid phase (28)
can be mixed (98) with the wet cake to increase the fat of the
DDGS.
[0132] United States ethanol producers are sensitive to the total
protein plus fat content ("ProFat") of DDGS as their customers, the
livestock growers, seek a threshold ProFat level for DDGS
incorporation into animal rations. The primary source of fat in
DDGS is residual oil from the fermented grain. Over the past
decade, growers have accepted DDGS with reduced fat content as
ethanol producers remove and sell more distillers oil. High protein
meals derived from distillers grains command significantly higher
prices than DDGS, and thus, although advantageous to the ethanol
producer, further decreases the ProFat value of DDGS.
[0133] In one embodiment of the present invention, distillers oil
can be fractionated to produce valuable lipid compositions, e.g. a
concentrate containing beneficial non-glyceride compounds. Any of
the recovered phases can be returned to the DDGS to help maintain
ProFat specifications. The concentrate can be further concentrated
in BNGs by removal of FFAs and glycerides, which can also be added
to DDGS to maintain ProFat content.
[0134] Thus, in one embodiment, distillers oil from a fermentation
facility is fractionated into the compositions of the present
invention, a valuable lipid composition is isolated, and some or
all of the remaining compositions can be incorporated into dry
distillers grains (DDG) or DDGS. The fractionation and isolation of
the lipid composition can be performed as described in the steps
above.
[0135] Therefore, in one embodiment, the process of the present
invention can be integrated or proximately located with a
fermentation facility such as an alcohol facility. Compositions of
the present invention can be removed from a lipid feedstock of the
fermentation facility/alcohol facility and added to other
co-products of the facility. The solvent and lipid feedstocks can
be products, co-products, by-products, or intermediates of the
fermentation facility. The solvent can be an alcohol or an
alcohol/water composition of product, co-product, and intermediate
stream of an alcohol fermentation facility. The solvent can be an
alcohol or an alcohol/water composition chosen from the group
consisting of product, co-product, and intermediate stream of an
alcohol fermentation facility. The alcohol or alcohol/water
composition can be recycled to the integrated or proximately
located fermentation facility after it is used in the production of
the lipid compositions. The lipid feedstock can be distillers oil,
such as distillers corn oil, obtained from a pre-fermentation or
post-fermentation process stream.
[0136] The present invention also provides for a method of
producing a distiller's product by separating a lipid from a
fermentation process, mixing the lipid with a solvent and obtaining
a lipid/solvent mixture, separating the lipid/solvent mixture into
two or more fractions, and adding at least some of the one or more
fractions to at least a portion of fermentation stillage. Each of
these steps are described above.
[0137] The invention is further described in detail by reference to
the following experimental examples. These examples are provided
for the purpose of illustration only, and are not intended to be
limiting unless otherwise specified. Thus, the invention should in
no way be construed as being limited to the following examples, but
rather, should be construed to encompass any and all variations
which become evident as a result of the teaching provided
herein.
Example 1--Ethanol and Methanol Extractions of DCO
[0138] A sample of distillers corn oil (DCO) produced by separation
from the stillage syrup using a disc stack centrifuge was obtained
from a corn ethanol plant. The DCO was extracted in the laboratory
with anhydrous ethanol and methanol as follows.
[0139] Method: Two 50 ml samples of DCO were accurately weighed
into separate 250 ml Erlenmeyer flasks, each flask containing a
magnetic stir bar and a weighed volume of approximately 50 ml
ethanol or methanol respectively. The flasks were stirred for 120
minutes at room temperature and then allowed to quiescently phase
separate for 60 minutes. The light phase containing the extract
from each flask was decanted and weighed. The heavy raffinate from
each flask was weighed. Solvent was removed from the light phase by
rotovap at 60 C under vacuum to produce a first concentrate. The
heavy raffinate was extracted twice more with 50 ml with fresh
ethanol or methanol respectively following the same extraction
procedure. A second and third concentrate was collected after
solvent removal by rotovap. The final raffinate (purified oil) and
a sample of the original DCO were also retained for analysis.
[0140] The concentration of carotenoids was determined by
absorbance at 445 nm of the sample dissolved in ethanol. The
glyceride and free fatty acid concentrations were determined by
correlating, to a standard calibration curve, the FT-IR absorbance
of the 1744 cm.sup.-1 peak for ester bond and the 1710 cm.sup.-1
for carboxylic acid peak, respectively.
[0141] Results: The results are shown in TABLE 1.
TABLE-US-00001 TABLE 1 Concentration of Carotenoids, Glycerides,
and FFAs Glycerides Free Fatty (TAGs + Acids Carotenoids DAGs)
(FFAs) % w/w % w/w % w/w DCO 0.03 88 12 Ethanol Purified Oil 0.02
98 2 (final raffinate) First Concentrate 0.13 62 38 (solvent free
extract) Methanol Purified Oil 0.03 98 2 (final raffinate) First
Concentrate 0.20 42 58 (solvent free extract)
[0142] The percentage of glycerides in the oil increased from 88%
in the feedstock (DCO) to 98% in the raffinate (purified oil) for
both methanol and ethanol extractions. The concentrate from
methanol and ethanol extractions both showed significantly higher
free fatty acid and carotenoid levels as compared with the DCO
feed. Both ethanol and methanol are polar solvents; however,
ethanol is more hydrophobic than methanol. The greater
hydrophobicity of ethanol resulted in increased levels of glyceride
oils (TAGS and DAGs) partitioning into the extract phase at the
expense of FFAs and carotenoids. Conversely, the lesser
hydrophobicity of methanol results in greater partitioning of FFAs
and carotenoids into a methanol extract phase versus ethanol.
EXAMPLE 1 demonstrates the effectiveness of polar solvents and that
the composition of the recovered oil fractions can be tailored
through proper solvent selection.
Example 2--Ethanol Extraction of DCO
[0143] A sample of distillers corn oil (DCO) produced as described
in EXAMPLE 1. The DCO was extracted twice with anhydrous ethanol at
a 3:1 solvent/feed mass ratio.
[0144] Method: Two 50 ml samples of DCO were accurately weighed
into separate 250 ml Erlenmeyer flasks, each flask containing a
magnetic stir bar and 150 ml ethanol. The flasks were stirred for
120 minutes at room temperature and then allowed to quiescently
phase separate for 30 minutes. The extract from each flask was
decanted, weighed and combined. The raffinate from each flask was
weighed and combined. Solvent was removed from the combined light
phase by rotovap at 60.degree. C. with vacuum to produce a first
concentrate. The combined raffinate phase was extracted again with
150 ml ethanol following the same extraction procedure and a second
concentrate was collected after solvent removal by rotovap. The
first and second concentrates were weighed, combined, and retained
for analysis. The final raffinate oil and a sample of the original
DCO were also retained for analysis. Analyses of sterols and
tocopherols were based on JAOCS Vol. 60, no. 8 (August 1983).
Analyses of FFAs, glycerides (MAG, DAG, TAG), tocotrienols and
carotenoids were performed by POS Bio-Sciences (Saskatoon,
Saskatchewan, Canada) using published and proprietary POS
Bio-Science methods as follows:
[0145] Free Fatty Acids: reference AOCS Ca 5.alpha.-40. Acyl
Glycerides: mono and diglycerides reference AOCS Cd 11d-96;
triglycerides by POS internal method, reference AOCS Official
Method Cd 11d-96. Tocotrienols: internal POS method, reference: M.
Balz et al., Fat Sci. Technol., 94 Jahrgang, Nr. 6, 1992, pp
209-213 and M Balz et al., Fat Sci. Technol., 95 Jahrgang, Nr. 6,
1993, pp 215-220. Carotenoids: internal POS method: reference AOAC
Official Method 970.64.; F. W. Quackenbush and R. L. Smallidge, J.
Ass. Offic. Anal. Chem., 69, 767 (1986); L. C. Sander, K. E.
Sharpless, N. E. Craft and S. A. Wise, Anal. Chem., 66, 1667
(1994).
[0146] Results
TABLE-US-00002 TABLE 2 Final Final Concentrate Raffinate (solvent
Compound Unit DCO (purified oil) free extract) Astaxanthin ppm 12
nd 26 Lutein ppm 125 nd 273 Zeaxanthin ppm 97 nd 196 Total
Carotenoids ppm 234 nd 495 alpha-Tocopherol ppm 170 0.07 280
beta-Tocopherol ppm 10 nd 70 gamma-Tocopherol ppm 990 0.21 208
delta-Tocopherol ppm 80 nd 110 Total Tocopherols ppm 1240 0.28 2600
alpha-Tocotrienol ppm 230 0.04 510 gamma-Tocotrienol ppm 360 0.05
690 delta-Tocotrienol ppm 10 nd 50 Total Tocotrienol ppm 600 0.09
1300 beta-Sitosterol ppm 768 545 1160 Stigmasterol ppm 89 52 157
Campesterol Ppm 314 199 521 Other Sterols ppm 673 499 976 Total
Sterols ppm 1844 1295 2814 Free Fatty Acids wt % 8.3 0.84 20.0 MAGs
wt % 0 nd 0.05 DAGs w % 1.28 0.27 2.91 TAGs wt % 86.0 99.3 66.5
[0147] The results of the experiment are shown in TABLE 2. With two
extraction stages, the percentage of triglycerides in the oil
increased from 86% in the feedstock (DCO) to over 99% in the
raffinate (purified oil) while reducing free fatty acids from over
8% to less than 1%. The two stage process also produced a
concentrate (solvent free extract) significantly enriched in free
fatty acids and the beneficial non-glyceride compounds of the
families carotenoids, tocopherols, tocotrienols and sterols. Many
of the BNGs were concentrated to more than twice their
concentrations in the starting feedstock.
Example 3--Bleached Raffinate
[0148] A sample of raffinate was produced as described in EXAMPLE
2. Raffinate was subjected to bleaching for color body removal.
[0149] Method: "Perform 6000" bleaching clay (Oil-Dri Corporation,
USA) was added to the oil at a 5% w/w ratio. The solution was
stirred and heated for 30 minutes at 93.degree. C. The sample was
centrifuged at 3000 g for 10 minutes. The supernatant was then
filtered through grade 3 filter paper (Whatman Co.) to remove
residual bleaching clay. The unbleached raffinate oil and resultant
bleached raffinate oil were bottled under nitrogen blanket and sent
to Craft Technologies for carotenoid analysis by their in-house
HPLC method utilizing a C18 column.
[0150] Results
TABLE-US-00003 TABLE 3 Analysis of Bleached Raffinate Unbleached
Bleached Raffinate Raffinate FFA (% w/w) not 1.3% determined Iodine
Value 121 121 MIU (% w/w) 3.24% 1.49% Carotenoids (ug/g)
trans-Lutein 33.3 0.02 Zeaxanthin 38.8 n.d. cis-Lutein/Zeaxanthin
19.5 n.d. alpha-Cryptoxanthin 8.8 n.d. beta-Cryptoxanthin 13.7 n.d.
alpha-Carotene 4.6 n.d. trans-beta-Carotene 5.5 n.d.
cis-beta-Carotene 3.3 n.d. Total Carotenoids 127.4 0.02 * n.d.: not
detected (detection limit = 0.005 .mu.g/g)
[0151] The results of the experiment are shown in TABLE 3. A
standard bleaching process applied to the raffinate reduced the
majority of the carotenoids to below detectable limits and total
carotenoids well below 1 ppm (1 ug/g).
Example 4--Further Concentration of Beneficial Non-Glyceride
Compounds by Shortpath Distillation (SPD)
[0152] A concentrate product from ethanol extraction of DCO was
prepared as described in EXAMPLE 2. The concentrate sample was
shipped to Myers Vacuum Inc. (Kittaning, Pa., USA) and distilled in
a Myers Lab-3 centrifugal molecular still. The feed was preheated
to 35 degrees C., loaded into a degasser and allowed to degas at 50
degrees C. until 30 mtorr was reached. The feed was then fed onto
the rotor (rotor temperature was 240 degrees C.) and yielded 23.6%
distillate and 76.4% residue. The distillate and bottoms fractions
were collected and analyzed for carotenoids and free fatty acids by
the methods of EXAMPLE 1.
[0153] Results
TABLE-US-00004 TABLE 4 Analysis of Shortpath Distillation Products
Carotenoid FFA mM % Concentrate (SPD feed) 0.577 29.8 SPD Bottoms
0.989 25.7 SPD Distillate 0.120 67.5
[0154] The results presented in TABLE 4 demonstrate that removal of
free fatty acids by shortpath distillation increases the carotenoid
concentration of the resultant distillate bottoms.
Example 5--Continuous Extraction
[0155] A sample of DCO was obtained as described in EXAMPLE 1. DCO
was heated to 70.degree. C. and fed to the bottom and room
temperature ethanol was fed to the top of a 10 ft by 4 inch
rotating disc liquid-liquid extraction column at approximately 0.3
L/min each. The extract phase was allowed to quiescently decant
overhead while raffinate was concurrently removed. Samples were
taken at various time points during operation and analyzed for
carotenoids as described in EXAMPLE 1.
[0156] Results
TABLE-US-00005 TABLE 5 Analysis of Continuous DCO-Ethanol
Extraction Carotenoid, mM Sample time, Extract min Feed (DCO)
Raffinate (solvent free basis) 30 0.581 0.374 1.267 60 0.581 0.419
1.201 90 0.581 0.383 1.381 120 0.581 0.435 1.141 150 0.581 0.444
1.364
[0157] EXAMPLE 5 demonstrates that continuous solvent extraction of
a lipid feedstock can consistently produce a concentrate (solvent
free extract) having double the initial DCO concentration of
carotenoids a beneficial non-glyceride compound.
[0158] Throughout this application, various publications, including
United States patents, are referenced by author and year and
patents by number. Full citations for the publications are listed
below. The disclosures of these publications and patents in their
entireties are hereby incorporated by reference into this
application in order to more fully describe the state of the art to
which this invention pertains.
[0159] The invention has been described in an illustrative manner,
and it is to be understood that the terminology, which has been
used is intended to be in the nature of words of description rather
than of limitation.
[0160] Obviously, many modifications and variations of the present
invention are possible in light of the above teachings. It is,
therefore, to be understood that within the scope of the appended
claims, the invention can be practiced otherwise than as
specifically described.
* * * * *