U.S. patent application number 11/600747 was filed with the patent office on 2007-06-07 for methods for concentration and extraction of lubricity compounds and biologically active fractions from naturally derived fats, oils and greases.
This patent application is currently assigned to Her Majesty in Right of Canada. Invention is credited to Philip Barry Hertz, Gabrielle Piette, Martin J. Reaney, Neil D. Westcott.
Application Number | 20070124992 11/600747 |
Document ID | / |
Family ID | 38091831 |
Filed Date | 2007-06-07 |
United States Patent
Application |
20070124992 |
Kind Code |
A1 |
Reaney; Martin J. ; et
al. |
June 7, 2007 |
Methods for concentration and extraction of lubricity compounds and
biologically active fractions from naturally derived fats, oils and
greases
Abstract
Methods for recovery of concentrates of lubricating compounds
and biologically active compounds from vegetable and animal oils,
fats and greases that allow separation of triglycerides, from
components with higher lubricity or biological activity or
enrichment protocols that increase the concentration of high
lubricity or biologically active compounds in the triglyceride. The
triglycerides are transesterified with a lower alcohol to produce
alkyl esters. Following the conversion process the esters are
separated from high molecular weight high lubricity compounds and
biologically active compounds by distillation. The esters have some
lubricity and may be sold as pollution reducing fuel components.
The high boiling point compounds that are the residues of
distillation, however, can either contribute significant lubricity
and may be used widely in lubricant applications or added to
petroleum fuels to decrease friction or the biologically active
components may be used in nutritional, cosmetic and therapeutic
applications. Therapeutic applications include use in human diets
to lower cholesterol.
Inventors: |
Reaney; Martin J.;
(Saskatoon, CA) ; Piette; Gabrielle; (Montreal,
CA) ; Hertz; Philip Barry; (Saskatoon, CA) ;
Westcott; Neil D.; (Saskatoon, CA) |
Correspondence
Address: |
Ralph A. Dowell of DOWELL & DOWELL P.C.
2111 Eisenhower Ave
Suite 406
Alexandria
VA
22314
US
|
Assignee: |
Her Majesty in Right of
Canada
|
Family ID: |
38091831 |
Appl. No.: |
11/600747 |
Filed: |
November 17, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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11290781 |
Dec 1, 2005 |
|
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|
11600747 |
Nov 17, 2006 |
|
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Current U.S.
Class: |
44/389 |
Current CPC
Class: |
C11B 1/06 20130101; C10M
105/34 20130101; C10M 2207/40 20130101; C11B 3/001 20130101; C10M
2207/2815 20130101; C11B 1/10 20130101; C10N 2070/00 20130101; C10L
1/1817 20130101; C10M 159/02 20130101; C10M 159/08 20130101; C11C
3/003 20130101; C10L 1/1802 20130101; C10L 1/19 20130101; C10M
177/00 20130101; C10L 10/08 20130101 |
Class at
Publication: |
044/389 |
International
Class: |
C10L 1/18 20060101
C10L001/18 |
Claims
1. A process for extracting lubricity enhancing and biologically
active compounds from oils, fats and greases, derived from animal
and plant sources, comprising pressing a solid source material so
as to release oils, fats and greases with lower levels of lubricity
enhancing compounds, and solvent extracting pressed solid source
material so as to produce a first oil, fat and grease concentrate
of lubricity enhancing and biologically active compounds
therefrom.
2. A process according to claim 1 including the steps of separating
said lower level of lubricity enhancing and biologically active
compounds from said pressed solid source material and mechanically
extracting a second oil, fat or grease concentrate with elevated
levels of lubricity enhancing and biologically active
compounds.
3. A process according to claim 2 including combining said first
and second concentrates.
4. A process according to claim 1 wherein triacyl glycerol
molecules present in the concentrate are chemically modified so as
to lower average molecular weight and distillation is utilized to
extract modified triglyceride products and leave a concentrate of
lubricity enhancing and biologically active compounds.
5. A process according to claim 3 where triacyl glycerol molecules
present in the concentrates are chemically modified to lower the
average molecular weight and distillation is utilized to extract
the modified triglyceride products and leave a concentrate of
lubricity enhancing compounds.
6. A process according to claim 1 where the fats are from tall
oil.
7. A process according to claim 1 wherein the plant source is
selected from the group consisting of soybean, canola, palm, olive,
hemp, sunflower, rapeseed, flaxseed, corn and coconut.
8. A process according to claim 1 wherein the animal source is
selected from the group consisting of swine, poultry and beef.
9. A lubricity enhancing concentrate, derived by extraction from a
source selected from animal and plant oils, fats and greases, and
enriched in dolichol, dolichol phosphate, phospholipids,
phospholipid metal ion complexes, diacylglycerides,
monoacylglycerides, sterols, sterol fatty acyl esters, tocopherols,
squalene, polyprenols, n-alkanols and wax esters.
10. A process according to claim 1 where triacyl glycerol molecules
present in the source material grease are converted to alkyl
esters, alcohols, amides, alkanes, aldehydes, fatty acids or amines
to lower the average molecular weight prior to distillation for
preparation of the lubricity concentrate.
11. A process according to claim 3 where triacyl glycerol molecules
present in the source material are converted to alkyl esters,
alcohols, amides, alkanes, aldehydes, fatty acids or amines to
lower the average molecular weight prior to distillation for
preparation of the lubricity concentrate.
12. A process according to claim 1 where high molecular weight
substances are separated from lower molecular weight substances by
size exclusion chromatography.
13. A process according to claim 1 where high molecular weight
substances are separated from lower molecular weight substances by
crystallization.
14. A process according to claim 1 where high molecular weight
substances are separated from lower molecular substances by any
combination of distillation, crystallization and
chromatography.
15. A process for enhancing lubricity characteristics of kerosene
comprising adding thereto a lubricity enhancing concentrate as
claimed in claim 9.
16. A process for enhancing lubricity characteristics of diesel
fuel comprising adding thereto a lubricity enhancing concentrate as
claimed in claim 9.
17. A process for enhancing lubricity characteristics of jet fuel
comprising adding thereto a lubricity enhancing concentrate as
claimed in claim 9.
18. A process for enhancing lubricity characteristics of gasoline
fuel for internal combustion engines comprising adding thereto a
lubricity enhancing concentrate as claimed in claim 9.
19. A process for enhancing lubricity characteristics of motor oil
comprising adding thereto a lubricity enhancing concentrate as
claimed in claim 9.
20. A lubricity enhanced kerosene product comprising kerosene and a
lubricity enhancing concentrate as claimed in claim 9.
21. A lubricity enhanced diesel fuel product comprising diesel fuel
and a lubricity enhancing concentrate as claimed in claim 9.
22. A lubricity enhanced jet fuel product comprising jet fuel and a
lubricity enhancing concentrate as claimed in claim 9.
23. A lubricity enhanced gasoline product comprising gasoline and a
lubricity enhancing concentrate as claimed in claim 9.
24. A lubricity enhanced motor oil product comprising motor oil and
a lubricity enhancing concentrate as claimed in claim 9.
25. A biologically active concentrate derived by extraction from a
source selected from animal and plant oils, fats and greases, and
enriched in dolichol, dolichol phosphate, phospholipids,
phospholipid metal ion complexes, diacylglycerides,
monoacylglycerides, sterols, sterol fatty acyl esters, tocopherols,
squalene, polyprenols, n-alkanols and wax esters.
Description
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is a Continuation-in-part of previously
filed U.S. patent application Ser. No. 11/290,781 filed 1 Dec.
2005
FIELD OF INVENTION
[0002] The present invention relates to methods for producing a
high lubricity fraction and for producing bioactive fractions from
fats, oils and greases derived from a wide variety of animal and
vegetable sources. In this specification, the terms "oils, fats and
greases" are used synonymously to describe starting materials
derived from vegetable and animal sources. Oils tend to be liquid
at room temperature and are derived from many biological sources
such as whales, fish and oil seed. Fats are generally solid at room
temperature and are derived from the same sources as oils. Greases
usually have high melting points and they may be synthetic
products. Some synthetic greases are plant derived, others are from
animals. The novel methods either separate lower lubricity
components of the fat, oil, or grease from higher lubricity
fractions or enrich the concentration of high lubricity components
or combine extraction and enrichment. In a preferred embodiment the
lower lubricity components are made volatile by chemical reactions
that split the triglyceride component of fat, oil, or grease. These
reactions may produce industrially useful products such as fatty
acid methyl esters, fatty acids, fatty alcohols, fatty aldehydes or
fatty amides of the original fat, oil, or grease which may be
separated from the higher lubricity components by distillation. The
lower lubricity components from fat splitting have inherent value
that is not diminished by the separation of the high lubricity
fraction. In fact, the low lubricity fraction may have increased
value as a result of the separation. The high lubricity fraction is
a collection of higher molecular weight substances present in the
fat, oil or grease or a modified component thereof. In another
preferred embodiment the high lubricity component of the fat, oil
or grease is separated from the triglyceride by absorption onto a
solid phase medium. Depending on the nature of the solid phase
extraction medium either the lower lubricity components or the
higher lubricity components are preferentially bound to the solid
phase extraction medium. The concentrate is then recovered from the
solid phase by extraction or from the liquid phase by evaporation.
In a further preferred embodiment the separation of higher
lubricity and lower lubricity components is achieved by
crystallisation from a solvent. In another embodiment of the
present invention the novel methods separate triglyceride
components of the fat, oil, or grease from biologically active
fractions. The methods also enrich the concentration of
biologically active components in a selective extraction process.
In a preferred embodiment the glyceride components are made
volatile by chemical reactions that split the oil triglyceride.
These reactions may produce industrially useful products such as
fatty acids, fatty acid esters, fatty alcohols, fatty aldehydes or
fatty amides of the original vegetable oil which may be separated
from the biologically active components by distillation. The
distilled components from fat splitting have inherent value that is
not diminished by the separation of the biologically active
fraction. In fact, the distilled components may have increased
value as a result of the separation. The biologically active
fraction is a collection of higher molecular weight substances
present in the starting material.
[0003] Extraction procedures may also be manipulated to improve the
content of compounds that impart lubricity to the fat, oil or
grease. In a preferred embodiment canola seed is mechanically
pressed to remove oil that has lower levels of the desired high
lubricity compounds. Mechanical extraction of the seed is followed
by solvent extraction that produces oil with a surprising level of
lubricity. The lubricity is imparted through the high ratio of
lubricity enhancing products to triglyceride extracted with the
oil.
[0004] Extraction procedures may also be manipulated to improve the
content of biologically active compounds. In a preferred embodiment
canola seed is mechanically pressed to remove oil that has lower
levels of the desired biologically active compounds. Mechanical
extraction of the seed is followed by solvent extraction of the
solids in a process that produces oil with a surprising level of
biologically active components.
[0005] Surprisingly it has also been discovered that specific
fractions of oil-bearing material may be selected that possess
higher levels of biologically active components. In a preferred
embodiment small seed is selected prior to extraction to enable
recovery of greater levels of the biologically active component.
The invention includes the selection of these materials by physical
and other methods.
BACKGROUND OF THE INVENTION
[0006] Since 1993, environmental legislation in the U.S. has
required that the sulfur content of diesel fuel be less than 0.05%.
In 2007 the sulfur content of diesel has been legislated to contain
less than 15 ppm sulfur. The reduction in the sulfur content of
diesel fuel has resulted in lubricity problems. It has become
generally accepted that the reduction in sulfur is also accompanied
by a reduction in polar oxygenated compounds and polycyclic
aromatics including nitrogen-containing compounds responsible for
the reduced boundary lubricating ability of severely refined (low
sulfur) fuels. While low sulfur content is not in itself a
lubricity problem, it has become the measure of the degree of
refinement of the fuel and thus reflects the level of the removal
of polar oxygenated compounds and polycyclic aromatics including
nitrogen-containing compounds.
[0007] Low sulfur diesel fuels have been found to increase the
sliding adhesive wear and fretting wear of pump components such as
rollers, cam plate, coupling, lever joints and shaft drive journal
bearings.
[0008] Concern for the environment has resulted in moves to
significantly reduce the noxious components in emissions when fuel
oils are burnt, particularly in engines such as diesel engines.
Attempts are being made, for example, to minimize sulfur dioxide
emissions by minimizing the sulfur content of fuel oils. Although
typical diesel fuel oils have in the past contained 1% by weight or
more of sulfur (expressed as elemental sulfur) it is now mandatory
to reduce the sulfur content to less than 15 ppm (0.0015%).
[0009] Additional refining of fuel oils, necessary to achieve these
low sulfur levels, often results in a reduction in the levels of
polar components. In addition, refinery processes can reduce the
level of polynuclear aromatic compounds present in such fuel
oils.
[0010] Reducing the level of one or more of the sulfur, polynuclear
aromatic or polar components of diesel fuel oil can reduce the
ability of the oil to lubricate the injection system of the engine.
As a result of poor fuel lubrication properties the fuel injection
pump of the engine may fail relatively early in the life of an
engine. Failure may occur in fuel injection systems such as
high-pressure rotary distributors, in-line pumps and injectors. The
problem of poor lubricity in diesel fuel oils is likely to be
exacerbated by future engine developments, aimed at further
reducing emissions, which will result in engines having more
exacting lubricity requirements than present engines. For example,
the advent of high-pressure unit injectors is anticipated to
increase the fuel oil lubricity requirement.
[0011] Similarly, poor lubricity can lead to wear problems in other
mechanical devices dependent for lubrication on the natural
lubricity of fuel oil.
[0012] Lubricity additives for fuel oils have been described in the
literature. WO 94/17160 describes an additive, which comprises an
ester of a carboxylic acid and an alcohol, wherein the acid has
from 2 to 50 carbon atoms and the alcohol has one or more carbon
atoms. Glycerol monooleate is an example. Although general mixtures
were contemplated, no specific mixtures of esters were
disclosed.
[0013] U.S. Pat. No. 3,273,981 discloses a lubricity additive being
a mixture of A+B wherein A is a polybasic acid, or a polybasic acid
ester made by reacting the acid with C.sub.1-C.sub.5 monohydric
alcohols; while B is a partial ester of a polyhydric alcohol and a
fatty acid, for example glyceryl monooleate, sorbitan monooleate or
pentaerythitol monooleate. The mixture finds application in jet
fuels.
[0014] U.S. Pat. No. 6,080,212 teaches of the use of two esters
with different viscosity in diesel fuel to reduce smoke emissions
and increase fuel lubricity. In one preferred embodiment of that
invention methyl octadecenoate, a major component of biodiesel, was
included in the formula. Similarly, U.S. Pat. No. 5,882,364 also
describes a fuel composition comprising middle distillate fuel oil
and two additional lubricating components. Those components being
(a) an ester of an unsaturated monocarboxylic acid and a polyhydric
alcohol and (b) an ester of a polyunsaturated monocarboxylic acid
and a polyhydric alcohol having at least three hydroxy groups.
[0015] The approach of using a two component lubricity additive was
pioneered in U.S. Pat. No. 4,920,691. The inventors describe an
additive and a liquid hydrocarbon fuel composition consisting
essentially of a fuel and a mixture of two straight chain
carboxylic acid esters, one having a low molecular weight and the
other having a higher molecular weight.
[0016] In U.S. Pat. No. 5,713,965 the synthesis of alkyl esters
from animal fats, vegetable oils, rendered fats and restaurant
grease is described. The resultant alkyl esters are reported to be
useful as additives to automotive fuels and lubricants.
[0017] Alkyl esters of fatty acids derived from vegetable
oleaginous seeds were recommended at rates between 100 to 10,000
ppm to enhance the lubricity of motor fuels in U.S. Pat. No.
5,599,358. Similarly a fuel composition was disclosed in U.S. Pat.
No. 5,730,029 comprising low sulfur diesel fuel and esters from the
transesterification of at least one animal fat or vegetable oil
triglyceride.
[0018] Most commercially available plant oils are highly enriched
in triacylglycerol and diacyl glycerols. However, as well as
including these more abundant substances, plant oils are known to
contain a large number of biologically active components. While the
biologically active components may occur at concentrations
sufficient to impart useful biological responses their
concentrations are often insufficient for many applications.
[0019] Phytosterols are known by those skilled in the art as
dietary materials that can lower blood serum cholesterol. In fact
knowledge that dietary phytosterols decrease cholesterol extend
back to 1951 (Peterson, Proc soc Exp Biol Med 1951; 78:1143). Jones
et al. (Can J Physiol Pharmacol 1997; 75:217) reports that
phytosterols are consumed at a level of 200-400 mg/day. However
clinical effects described in many publications are significant
when phytosterols or their esters are utilised at concentrations
well above the natural concentrations found in vegetable oils. For
example Shin et al. (Nutritional Research 2003; 23:489) provided
human test subjects with a beverage containing 800 mg/serving and
with 2-4 servings/day. The eight-week protocol significantly
lowered cholesterol in the test population.
[0020] Sterols occur at significant concentrations in many
vegetable oils mainly as free sterols and as their fatty esters.
Nevertheless, the concentrations found in most sources are less
than sufficient to produce a therapeutic effect.
[0021] Meguro et al. (Nutrition 2003; 19:670-675) report that
diacylglycerols interact with sterol provided in the diet to reduce
cholesterol levels in New Zealand White (NZW) rabbits below that
achieved by the same content of sterol in triacyl glycerol. They
hypothesise that the diacyl glycerol interacts with the sterol
partially through the higher solubility of the sterol in the diacyl
glyceride phase.
[0022] Dolichol is a naturally occurring high molecular weight
alpha-saturated polyprenol that is widely distributed in living
organisms. Mammals synthesise dolichol in normal metabolism but may
take it up from the diet as well (Jacobsson et al. 1989; FEBS
255:32). U.S. Pat. No. 4,599,328 teaches that dolichol is an
effective treatment for hyperuricuria, hyperlipemia, diabetes and
hepatic disease. It has also been demonstrated in animal model
systems that dolichol and dolichol phosphate can act as
antihypertensive treatments (U.S. Pat. No. 4,175,139).
[0023] Polyisoprenol compounds are similar to dolichol in structure
but serve a different function in metabolism. Polyisoprenol
compounds are widely distributed and known to be components of many
vegetable oils.
[0024] Tocols are an important class of nutrients and includes the
essential nutrient vitamin E or alpha tocopherol. While vitamin E
has a wide range of metabolic functions that are realised at low
rates of incorporation in the diet supplementation with vitamin E
is believed to have potential benefits in the prevention of ageing
and disease. While vegetable oils are significant sources of
vitamin E in the diet levels may be inadequate to meet recommended
daily allowances and recommended levels for therapeutic
effects.
[0025] Plant oils also contain chromanols including ubiquinone,
ubiquinol, plastoquinone and plastoquinol. These compounds are
potent antioxidants and are thought to slow ageing processes.
[0026] Carotenoids and notably lutein and zeazanthin are important
constituents of certain vegetable oils. Consumption of these
carotenoids has been associated with the prevention of specific eye
diseases. For example, an inverse association has been noted with
the incidence of advanced, neovascular, age-related macular
degeneration (AMD) and the dietary intake of lutein and zeaxanthin.
Individuals whose diets are modified to include an increased intake
of lutein and zeaxanthin generally respond with an increase in
concentrations in these pigments in their serum and maculae
(Hammond et al. 1997; Invest. Opthamol. Vis. Sci. 38:1795).
[0027] Typically phytosterol and vitamin E are obtained from
industrial streams encountered in the processing of plant based
oils. A phytosterol and tocopherol rich fraction is recovered
during the refining of vegetable oil where in a late stage of
refining vegetable oil is steam distilled under vacuum to deodorise
the oil. The deodoriser concentrate is rich in free fatty acid,
free sterol and tocopherol and substantially devoid of sterol
ester, dolichol, diacylglycerol and carotenoids. This fraction is a
major source of sterol and tocopherol used in nutritional
applications.
[0028] Phytosterol is also derived from the pulp and paper industry
where solution from alkali washed wood pulp is acidified to produce
a complex mixture of plant lipids known as tall oil. This latter
fraction can be divided to produce fatty acids, rosin acids and
sterols.
[0029] Carotenoids used for dietary purposes may be derived from a
number of sources. For example, marigold may be harvested and
processed as a source of dietary lutein. Other dietary carotenoids,
including astaxanthin and canthaxanthin are synthesised by
classical organic synthetic methods.
[0030] While vegetable oils may be rich sources of sterol esters,
tocols, and carotenoids methods of recovery of these components are
inefficient and products must be fractionated and reformulated for
use.
SUMMARY OF THE INVENTION
[0031] It is known by those skilled in the art that fuel additives
that enhance lubricity may be produced that contain lower alkyl
esters of fats, oils and greases yet surprisingly it is revealed,
in the present invention, that these mixtures contain ingredients
with substantially higher lubricity. Furthermore methods are
disclosed to efficiently recover these high lubricity components.
In preferred methods the triglyceride components of the fat, grease
or oil are converted to lower molecular weight compounds such as
fatty acids, fatty amides or fatty acid alkyl esters. In forming
the lower molecular weight compound it becomes possible to readily
separate the bulk material from the high lubricity components by
distillation. In a preferred embodiment the fat, oil or grease is
transesterified to produce a lower alkyl ester using methods known
to those skilled in the art. The ester is then distilled and
recovered for other purposes and the column bottoms of distillation
are recovered and refined to remove free acids formed in
distillation. The refined column bottoms recovered from the
distillation have substantial efficacy as lubricity additives. In a
preferred embodiment the fat, oil or grease is converted to fatty
acids. The fatty acids are then distilled and recovered for other
purposes and the column bottoms of distillation are recovered and
refined to remove residual free acids formed in distillation. The
refined column bottoms also have substantial efficacy as lubricity
additives. The lubricity concentrate comprises a complex mixture of
phospholipid, sterol, tocol, quinone, polyisoprene and
polyisoprenol and other lipid soluble components. In a preferred
embodiment of the present invention where the concentrate is an
enriched concentrate of lipid substances with molecular weights
greater than 400.
[0032] While the present invention may be accomplished through fat
splitting or other chemical modification followed by
crystallisation or distillation as preferred methods of
concentrating the lubricity fraction, other methods of
concentrating specific classes of oil soluble compounds from
triglyceride are also acceptable. For example, those skilled in the
art will recognise that it is possible to recover enriched
fractions from fats, oils and greases by solid phase extraction and
chromatographic methods. Solid phase extraction may be combined
with chemical modification steps or the chemical modification may
be forgone in the process of preparing the high lubricity
concentrates.
[0033] Furthermore we have made the surprising discovery that the
method of processing the oil may also act to concentrate the oil
soluble components that impart lubricity. Processing conditions may
be modified to enhance the extraction of high lubricity minor
components of oilseed and animal fat. The present invention
includes pre-extraction treatments that enhance either or both the
concentration of high lubricity components in oils.
[0034] In another preferred embodiment of the present invention
where the concentrate is enriched in dolichol, other polyisoprenols
and their derivatives, and the present invention describes methods
of optimally-preparing concentrates of biologically active oil
soluble compounds. In the preferred art the triglyceride components
of vegetable oils are subject to chemical rearrangements to form
new products that have a lower molecular weight and boiling point.
Reaction conditions are selected so as to prevent the degeneration
of the biologically active components. It has been found that the
process of distillation under mild conditions can remove much of
the modified glyceride product leaving behind a concentrate of
biologically active substances. As most plant oils are sources of
carotenoid, phytosterol, tocol, chromanol, and dolichol and these
components have relatively high molecular masses it is common to
find these compounds present in the concentrate.
[0035] In a preferred embodiment ethyl esters were synthesised
using an alkaline catalyst reaction of ethanol with low erucic acid
rapeseed oil, a plant oil that is highly rich in triglyceride. In
this embodiment the reaction conditions are maintained under the
mildest possible conditions to prevent the destruction of the
biologically active components. After the reaction the glycerol
released in the reaction and excess ethanol were removed, the
esters were distilled in a thin film still to recover over 90
percent of the ethyl ester as a concentrate. The resulting
concentrate was highly enriched in phytosterol, tocol, dolichol and
carotenoid.
[0036] The instant invention also includes methods of
pre-extraction that produce enriched concentrates of biologically
active compounds. In a preferred embodiment low erucic acid
rapeseed was crushed mechanically using a commercial expeller press
under mild conditions to recover an oil fraction that had reduced
levels of biologically active components. The mild conditions of
mechanical extraction are known to those skilled in the art as cold
pressing. After mechanical extraction the solid fraction was
subject to solvent extraction to recover the remaining oil. The
second oil possessed elevated concentrations of many biologically
active components including phytosterol, tocol, dolichol and
carotenoid. Although the triglyceride remained a major component of
the solvent extracted oil the concentration step allowed for the
use of more efficient process steps in the production of a
concentrate of biologically active components. It is a particular
benefit of this latter preferred embodiment that the manufacturing
process generates a significant fraction of oil that has not been
extracted by utilising a solvent.
DETAILED DESCRIPTION OF THE INVENTION
[0037] Vegetable oils, such as tall, soybean, canola, palm,
sunflower, hemp, rapeseed, flaxseed, corn or coconut, are a complex
mixture of molecular components of which triglycerides are usually
the most abundant component. Numerous other seed oils are known and
are also included in this invention. Palm and olive oil are derived
by processing the fruits of the palm and olive trees. Tall oil is a
vegetable oil recovered from the pulp and paper industry and is
essentially the oil present in wood. Similarly, animal fats and
greases, such as those derived from swine, poultry and beef, are
predominantly triglyceride in composition. Triglycerides are
triesters of glycerol and carboxylic acids that have great
industrial importance. In industry triglycerides are reacted with
water to form fatty acids, hydrogen to form fatty alcohols,
reducing agents to form aldehydes, amines to form fatty amides and
alcohols to form alkyl esters. Triglycerides have relatively high
molecular weights, usually greater than 800 amu and thus are
difficult to distill. However, fatty acids, fatty amides, fatty
alcohols and fatty alkyl esters of lower alcohols have lower
molecular weights and are readily distilled under vacuum. The
residue left after vacuum distillation is a concentrate of
substances with molecular weights above those of the fatty acid,
amide, alcohol, aldehyde or ester.
Preconcentration
[0038] The oilseeds are typically processed both by mechanical and
solvent extraction to recover the seed oil. Mechanical extraction
methods include hydraulically operated oil presses, continuous
screw presses, and extruders adapted for oil extraction. Mechanical
extraction methods mobilise a portion of the oil by both shear and
pressure which ruptures oil containing structures in the seed. Once
the oil is mobilised it may flow away from the solids which are
held in the press by physical structures such as metal bars.
Depending on the severity of the pressure, temperature and shear
conditions the amount of oil recovered from oilseed varies. In
order to maximise the yield of oil it is possible to utilise more
severe extraction conditions. It is common to those skilled in the
art to utilise expeller presses in sequence to first remove a
portion of the oil under milder extraction conditions then to
follow this by a second expeller press treatment under more severe
conditions. It is an example of the current art where the total
pressed oil is utilised for recovery of biologically active
components. It is a preferred embodiment of the present invention
that the oil recovered from the second oilseed press is utilised as
a superior source for the biologically active materials. In
advanced expeller press designs it is common to increase the
severity of pressing of the oilseed material as it passes along the
press. Oil recovered from the early portion of the press is
extracted under milder conditions than material recovered from the
latter stages of the press. Surprisingly it has been found that the
level of biologically active oil soluble ingredients is enriched in
the oil recovered in the latter stages of pressing. It is a
preferred embodiment of the present invention that the oil
recovered from the latter stages of a press is recovered and
utilised for extraction of the biologically active fraction. It is
also common practise in industry to utilise an expeller press to
remove a portion of the oil followed by placing the partially
deoiled seed meal in a continuous or batch solvent extraction
vessel. The seed meal may then be fully deoiled by extracting with
a suitable non-polar solvent. Useful solvents include but are not
limited to hexane, supercritical carbon dioxide, propane, ethanol,
isopropanol and acetone. It is an embodiment of the present
invention that oil recovered by solvent extraction, following
mechanical removal of the oil is utilised as a superior source of
the biologically active materials.
Molecular Weight Reduction: Transesterification
[0039] Once the oil has been separated, it is an object of the
current invention to produce a useful concentrate of the
biologically active fraction. In order to concentrate the
biologically active molecules it is necessary to separate them from
the higher molecular weight and often less biologically active
triglyceride materials as they may constitute over 95 percent of
the seed oil. Typical seed oil glycerides have molecular masses of
greater than 800 g/mole. As such these compounds are difficult to
distill. In the current art to achieve this separation it is
necessary to convert the triglyceride oils to lower molecular
weight forms so that they are readily distilled to leave a residue
of the biologically active concentrate.
[0040] Glycerides are esters of glycerol and they are readily
reacted to produce fatty compounds that have lower molecular weight
than the parent glyceride. In a preferred embodiment of the current
invention the glyceride component of the seed oil is converted to
fatty acid esters. There are many documented approaches to the
chemical conversion of triglycerides to alkyl esters known by those
skilled in the art and such approaches other than those described
herein are included in the instant invention. In a preferred
embodiment vegetable oil that contains biologically active
compounds is treated with a solution of an alkali base, such as
potassium hydroxide dissolved in ethanol under anhydrous
conditions. The ensuing reaction converts the triglyceride to the
corresponding ethyl ester. After conversion, the molecular weight
of the fatty ester compounds is substantially reduced while the
biologically active components with higher molecular weights are
not similarly reduced in molecular mass. Distillation will
selectively remove the fatty ester compounds and leave a unique
residue of biologically active materials with higher molecular
weights. While the use of distillation is preferred for separation
of the alkyl ester component of the reaction it is obvious to one
skilled in the art that other methods of separating molecules that
differ in size that could be used to separate the alkyl esters from
the biologically active fraction. These methods are included in the
present invention. As the products of the current invention may be
produced using ethanol, the use of other lower alkanols with
between 1 and 5 carbon atoms is included as a portion of the
current art.
Molecular Weight Reduction: Hydrolysis
[0041] In a preferred embodiment of the current invention the
glyceride component of the seed oil is converted to fatty acids.
There are many documented approaches to the chemical conversion of
triglycerides to fatty acids known to those skilled in the art and
such approaches other than those described herein are included in
the instant invention. In a preferred embodiment vegetable oil that
contains biologically active compounds is treated with water and a
suitable catalyst. The ensuing reaction converts the triglyceride
to the corresponding fatty acids. After the conversion the
molecular weight of the fatty acid compounds is substantially
reduced while the biologically active components with higher
molecular weights are not similarly reduced in molecular mass.
Distillation will selectively remove the fatty acid compounds and
leave a unique residue of biologically active materials with higher
molecular weights. While the use of distillation is preferred for
separation of the fatty acid component of the reaction it is
obvious to one skilled in the art that other methods of separating
molecules that differ in size that could be used to separate the
fatty acids from the biologically active fraction. These methods
are included in the present invention. The products of the current
invention may be produced using enzymatic, organic and mineral
catalysts and as these catalysts are known to those skilled in the
art of lipid chemistry they are included as a portion of the
current art.
Molecular Weight Reduction: Saponification
[0042] In a preferred embodiment of the present invention the
glyceride component of the seed oil is converted to soaps which may
be acidulated to release fatty acids. There are many documented
approaches to the chemical conversion of triglycerides to soaps
known by those skilled in the art and such approaches other than
those described herein are included in the present invention. In a
preferred embodiment vegetable oil that contains biologically
active compounds is treated with water and a suitable base. The
ensuing reaction converts the triglyceride to the corresponding
soap. After the conversion the soaps may be converted by the
addition of a suitable acid to yield a solution of fatty acids and
the biologically active fraction. The molecular weight of the fatty
acid compounds is substantially reduced while the biologically
active components with higher molecular weights are not similarly
reduced in molecular mass. Distillation will selectively remove the
fatty acid compounds and leave a unique residue of biologically
active materials with higher molecular weights. While the use of
distillation is preferred for separation of the fatty acid
component of the reaction it is obvious to one skilled in the art
that other methods of separating molecules that differ in size
could be used to separate the fatty acids from the biologically
active fraction. These methods are included in the instant
invention. The products of the current invention may be produced
using a wide range of alkali materials known to those skilled in
the art of lipid chemistry; the use of these materials is included
as a portion of the current art.
Molecular Weight Reduction: Reduction
[0043] In a preferred embodiment of the current invention the
glyceride component of the seed oil is converted to fatty alcohols.
There are many documented approaches to the chemical conversion of
triglycerides to fatty alcohols known by those skilled in the art
and such approaches other than those described herein are included
in the instant invention. In a preferred embodiment vegetable oil
that contains biologically active compounds is treated with
metallic potassium in butanol. The ensuing reaction converts the
triglyceride to the corresponding alkanol. The molecular weight of
the fatty alcohol compounds is substantially reduced while the
biologically active components with higher molecular weights are
not similarly reduced in molecular mass. Distillation will
selectively remove the fatty alcohol compounds and leave a unique
residue of biologically active materials with higher molecular
weights. While the use of distillation is preferred for separation
of the fatty alcohol component of the reaction it is obvious to one
skilled in the art that other methods of separating molecules that
differ in size could be used to separate the fatty alcohols from
the biologically active fraction. These methods are included in the
present invention. The products of the current invention may be
produced using other alkali metals and by other reactions known to
those skilled in the art of lipid chemistry; the use of these
reactants and catalysts is included in the present invention.
Distillation
[0044] Wide ranges of distillation processes are known to those
skilled in the art of lipid chemistry. It is known that lipid
molecules are sensitive to damage by exposure to high temperatures
encountered in distillation and as such distillation processes that
minimise temperature exposure are preferred. Vacuum speeds
distillation and minimises exposure to heat. Stills that operate
under vacuum are thus preferred. Examples of preferred processes
also include continuous distillation methods including but not
limited to molecular distillation, thin film distillation and other
short path and continuous distillation processes.
Size Exclusion Chromatography
[0045] It is also possible to separate compounds utilising size
exclusion chromatography. In a preferred method higher molecular
weight biologically active compounds are separated from lower
molecular weight fatty compounds by passage over suitable size
exclusion media. Examples of suitable media include but are not
restricted to Sephadex LH-20 and Styragel GPC.
Measurement of Carotenoid
[0046] Carotenoids can be measured in whole vegetable oil and in
concentrates by the presence of specific peaks in the visible range
of the spectrum using a suitable spectrophotometer. The carotenoid
content can be estimated utilising a standard curve prepared from a
pure standard. Carotenoids were estimated on the basis of either
beta carotene or lutein standards.
Measurement of Sterol
[0047] Sterol content was determined by non-destructive NMR
analysis. In this procedure the oil or biologically active
concentrate was dissolved in deuterated chloroform and the proton
spectrum was recorded using a 400 MHz Bruker Spectrospin
spectrometry. Based on standard curves established on solutions of
phytosterol free esters and cholesterol it was determined that
spectrometry could reliably determine the concentration of sterols
in vegetable oil samples.
[0048] GC-FID and GC-MS was used to determine sterol concentration
in fatty acids and esters.
Measurement of Tocopherol
[0049] GC-FID and GC-MS was used to determine tocopherol
concentration in fatty acids and esters.
Measurement of Squalene
[0050] GC-FID and GC-MS was used to determine squalene
concentration in fatty acids and esters.
Measurement of Dolichol
[0051] LC-MS was used to determine the presence of dolichol in
fatty acid, ester and
Lubricity Measurements:
Laboratory Method:
[0052] Lubricity is measured using a Munson Roller On Cylinder
Lubricity Evaluator (M-ROCLE; Munson, J. W., Hertz, P. B., Dalai,
A. K. and Reaney, M. J. T. Lubricity survey of low-level biodiesel
fuel additives using the "Munson ROCLE" bench test, SAE paper
1999-01-3590). The M-ROCLE test apparatus conditions are given in
Tablel. During the test, the reaction torque was proportional to
the friction force produced by the rubbing surfaces and was
recorded by a computer data acquisition system. The recorded
reaction torque was used to calculate the coefficient of friction
with the test fuel. The image of each wear scar produced on the
test roller was captured by a video camera mounted on a microscope
and was transferred to image processing software, from which the
wear scar area was measured. After determining the unlubricated
Hertzian contact stress, a dimensionless lubricity number (LN),
indicating the lubricating property of the test fuel, was
determined using the following equation:
LN=.circle-solid..sub.ss/.circle-solid..sub.H.circle-solid..sub.ss;
.circle-solid..sub.ss=P/A Where: [0053]
.circle-solid..sub.ss=steady state ROCLE contact stress (mPa);
[0054] .circle-solid..sub..circle-solid. .circle-solid. Hertzian
theoretical elastic contact stress (mPa);
[0055] Kerosene Reference Fuel was Escort Brand 1-K Triple
Filtered, Low Sulfur, Canadian Tire Stock No. 76-2141-2, Lot 135,
BO2943. Each fuel ester sample was lubricity tested six times on
the machine followed by a calibration of the reaction torque.
TABLE-US-00001 TABLE 1 M-ROCLE TEST CONDITIONS Fuel temperature,
.degree. C. 25 .+-. 1.5 Fuel capacity, mL 63 Ambient temperature,
.degree. C. 24 .+-. 1.0 Ambient humidity, % 35-45 Applied load, N
24.6 Load application velocity, mm/s 0.25 Test duration, min 3 Race
rotational velocity, rpm 600 Race Surface velocity, m/s 1.10 Test
specimens Falex test cylinder, F-S25 test rings, SAE 4620 steel
Outer diameter, mm 35.0 Width, mm 8.5 Falex tapered test rollers,
F-15500, SAE 4719 steel Outer diameter, mm 10.18, 10.74 Width, mm
14.80
Field Test Method:
[0056] Motor oil analysis was utilized to infer engine wear. This
involved high-resolution Inductively Coupled Plasma (ICP)
Spectrometry analysis of the used oil wear particles and oil
additive elements. Ferrography, and magnetic particle analysis was
determined for larger (>5 .mu.m) wear particles. Physical and
chemical analyses of oil viscosity, acid neutralizing-ability
(Total Base Number (TBN) and Total Acid Number (TAN)), and any
dilution by fuel, water, or glycol was also monitored. An
independent laboratory, Fluid Life Corporation in Edmonton Alberta,
conducted these analytical tests.
[0057] All motor oil analysis data was adjusted to calculate true
wear rates considering oil volumes present in the crankcase, oil
consumed, sample volumes, and oil additions. All wear metals were
monitored, with engine wear iron examined most critically. As well,
by sectioning the filters after each oil change, filter wear and
contaminant particles were microscopically and spectrographically
compared. Field test logs indicating daily ambient minimum and
maximum temperatures, numbers of cold and hot starts, ratios of
city to highway driving, and liters of fuel consumed were
tabulated. Consistent driving styles were enforced. Fuel economy
and any operational difficulties were noted throughout the test
program. Esso brand regular unleaded gasoline and Pennzoil
Multigrade SJ motor oils were used throughout the study. The canola
additives were prepared or obtained as described in specific
examples.
Calculation of True Wear Rate
[0058] Consider for example, a vehicle engine that operates
"normally" or "ideally", generating and depositing in the crankcase
oil a constant 10 parts per million (10 ppm) of iron (Fe) in every
1,000 km of operation. Its "true wear rate" would be calculated by
dividing the particle count by the distance traveled, yielding 10
ppm/1,000 km. Here, round numbers have been used to assist the
reader in understanding the procedure. If the vehicle were operated
for 10,000 km under uniform conditions the wear iron level would
rise 10 fold to 100 ppm Fe. This rise in ppm could start from zero
ppm for an initially "flushed clean" engine, or more often from
some initial "reference" level, taken shortly after an oil change.
A typical oil and filter change typically leaves 10% to 15% of the
used oil behind, so referencing is an important initial first step
in a comparative engine wear analysis.
[0059] If the crankcase capacity of the example engine is 10 L, the
amount of elemental iron deposited in the oil after 10,000 km can
be calculated as follows:
[0060] The 100 ppm Fe is present in the 10 L crankcase volume.
[0061] Therefore the iron wear volume is obtained by multiplying
the iron concentration by the oil volume: 100 parts
Fe(10.sup.-6).times.10 L=1,000 .mu.L Fe.
[0062] This 1,000 .mu.L Fe is the engine wear volume under ideal
10,000 km conditions.
[0063] If the engine oil was referenced at, say 70 km, and found to
contain 10 ppm Fe, this would cause the final test reading after
the 10,000 km to be 10 ppm higher: 100 ppm+10 ppm=110 ppm.
[0064] So to correct for initial residual iron one must subtract
the reference ppm from the final test ppm, to obtain the "net" wear
iron, which in this case is still: 110 ppm-10 ppm=100 ppm.
[0065] Oil sampling itself requires a small amount of oil
(.about.200 mL) to be withdrawn from the crankcase each time the
wear metals are monitored.
[0066] Assume 5 oil samples of 0.2 L=1.0 L of oil was removed
during the 10,000 km run. The average net ppm Fe concentrations in
these 5 samples would be close to the average net crankcase
concentration of 50 ppm, which started at 0 ppm and ended at 100
ppm.
[0067] This oil sampling has caused two things to happen: [0068]
(a) There is now 1.0 L less oil in the 10.0 L crankcase due to the
sampling, i.e. 9.0 L. [0069] (b) 1.0 L of oil containing, on net
average, .about.50 ppm Fe has been removed.
[0070] The indicated final net test value would no longer equal 100
ppm Fe but can be calculated by doing a wear iron balance on the
removal of iron activity as follows: (100 ppm.times.10 L)-(50
ppm.times.1 L)=Test Fe ppm.times.9 L,
[0071] Solving for the Test Iron level in ppm, we obtain: Test
ppm=(1000 .mu.L Fe-50 .mu.L Fe)/9 L, Test ppm=950 .mu.L/9L=105.5
ppm Fe.
[0072] Due to sampling the "wear rate" based on the final test
value of 105.5 ppm Fe, instead of the true net previous 100.0 ppm
value, would be calculated in error as too high at: 105.5 ppm
Fe/10,000 km, or, 10.55 ppm Fe/1000 km.
[0073] To compensate for sampling, "adding back" the oil sample
volumes with new oil, each time a sample was taken, could be tried.
New oil may contain small levels of wear metals (0.0-2.0 ppm Fe)
and high levels of additive metals (800-1200 ppm Zn).
[0074] Focusing, for now, on the iron, we can do another iron
balance taking into account the 1.0 L sampling volumes and the 1.0
L add-back volumes (at 1 ppm Fe for new oil) as follows, starting
with the previous true wear iron level: (100 ppm.times.10 L)-(50
ppm.times.1 L)+(1 ppm.times.1L)=Test ppm.times.10 L (Eq. 1) Test
ppm=(1000 .mu.L Fe-50 .mu.L Fe+1 .mu.L)/10 L Test ppm=951/10=95.1
ppm Fe After taking samples, and adding oil back, the indicated
wear rate result based on the final sample is now too low, at 95.1
ppm Fe/10,000 km or 9.51 ppm Fe/1000 km.
[0075] If an engine "uses" oil, this volume will be similar to us
taking out oil samples. If the oil is "topped-up" to the full mark,
this is like adding back new oil after sampling. If the crankcase
ends up below or above "full", this can also be taken into account
with reference to the previous two examples.
[0076] It is desired to calculate the "true ppm" based on a "test
ppm" wear indication. In more general terms the previous iron
balance (Eq. 1) can be rewritten as follows: (True ppm.times.Start
L)-(True ppm.times.Used L/2)+(New ppm.times.Add L)=Test
ppm.times.Test L True .times. .times. ppm = ( Test .times. .times.
ppm .times. Test .times. .times. L ) + ( True .times. .times. ppm
.times. Used .times. .times. L / 2 ) - ( New .times. .times. ppm
.times. Add .times. .times. L ) - Start .times. .times. L ( Eq .
.times. 2 ) ##EQU1## For True ppm, we can approximate the True ppm
in the second term of (Eq. 2) equal the Test ppm, to get (Eq. 3):
True .times. .times. ppm = ( Test .times. .times. ppm .times. Test
.times. .times. L ) + ( Test .times. .times. ppm .times. Used
.times. .times. L / 2 ) - ( New .times. .times. ppm .times. Add
.times. .times. L ) - Start .times. .times. L ( Eq . .times. 3 )
##EQU2## Using the Test 95.1 ppm value from the example above, and
substituting into (Eq. 3), yields a reasonably good True Fe value,
close to the known 100.0 ppm, as: True Fe .times. .times. ppm = (
95.1 .times. .times. ppm .times. 10 .times. .times. L ) + ( 95.1
.times. .times. ppm .times. 1 .times. .times. L / 2 ) - ( 1 .times.
.times. ppm .times. 1 .times. .times. L ) 10 .times. .times. L =
99.75 .times. .times. ppm ##EQU3## If a higher accuracy is required
this 99.75 ppm value can be substituted for the Test ppm yielding:
True Fe .times. .times. ppm = ( 95.1 .times. .times. ppm .times. 10
.times. .times. L ) + ( 99.75 .times. .times. ppm .times. 1 .times.
.times. L / 2 ) - ( 1 .times. .times. ppm .times. 1 .times. .times.
L ) 10 .times. .times. L = 99.99 .times. .times. ppm ##EQU4##
Therefore the following, repeated, Equation 3 can be used to
calculate "True Wear" or "Normalize" indicated lubricant test
results based on oil volumes used or sampled, crankcase capacity,
new oil added, or any combination of the above: True .times.
.times. ppm .times. ( Test .times. .times. ppm .times. Test .times.
.times. L ) + ( Test .times. .times. ppm .times. Used .times.
.times. L / 2 ) - ( New .times. .times. ppm .times. Add .times.
.times. L ) - Start .times. .times. L ( Eq . .times. 3 )
##EQU5##
EXAMPLES
Example 1
Two Stage Transesterification of Canola Oil with Methanol and
Potassium Hydroxide
[0077] Methyl esters of canola oil, also known to those skilled in
the art as low erucic acid rapeseed oil, were prepared using a
two-stage base catalysed transesterification. The two-stage
reaction was required to remove glyceride from the final product.
Prior to the reaction the catalyst was prepared by dissolving
potassium hydroxide (10 g) in methanol (100 g). The catalyst
solution was divided into two 55 g fractions and one fraction was
added to 500 g of canola oil (purchased from a local grocery store)
in a 1 L beaker. The oil, catalyst and methanol were covered and
stirred vigorously for 1 hour on a stirring hot plate by the
addition of a teflon stirring bar. After stirring, the contents of
the beaker were allowed to settle for 2 hours. At this time a
cloudy upper layer and a viscous lower layer had separated. The
layers were separated using a seperatory funnel and the upper layer
was mixed with the remaining potassium hydroxide in methanol
solution. This second mixture was stirred vigorously in a covered
beaker for 1 hour and allowed to settle overnight. The mixture
settled to form two layers. The upper layer was collected using a
seperatory funnel and used for further refining steps.
Example 2:
Two Stage Transesterification of Tallow with Methanol and Potassium
Hydroxide
[0078] Tallow was collected from a renderer. Five hundred grams of
tallow were heated to 40.degree. C. prior to esterification to
liquify the solid mass. Thereafter, all processes and conditions
were identical to those described in example 1.
Example 3:
Refining and Distillation of Canola Oil Methyl Ester
[0079] Canola methyl ester prepared in example 1 was refined to
remove methanol, glycerol, soaps and other compounds that might
interfere with distillation. Methanol was removed under vacuum
(28.5'') by a rotary vacuum evaporator equipped with a condenser.
The methyl esters were maintained at 50.degree. C. for 30 minutes
to thoroughly remove alcohol. After evaporation the esters were
treated with silica (0.25% w/w Trisyl 600; W. R. Grace Co.) and
stirred at room temperature for 1 hour. After silica treatment
methyl esters were filtered over a bed of Celite to remove both
silica and other materials.
[0080] After refining the methyl esters, fractional high vacuum
distillation was performed using a simple distillation apparatus. A
vacuum of less than 1 mm was maintained throughout the procedure.
During fractionation temperatures at the top of the column, before
the condenser, were between 120.degree. C. and 140.degree. C. The
distillation apparatus included a liquid nitrogen cooled vapour
trap, which allowed the attainment of high vacuum conditions.
Approximately 500 mL of distillate (about half the sample) was
obtained and then the heating mantle was removed while maintaining
the apparatus under vacuum. Vacuum was then broken and fractions of
both distillate and bottoms were obtained for further studies.
Distillation was then resumed until a further 200 mL of distillate
were obtained (about half the sample). The apparatus was again
chilled, vacuum was broken and samples of 100 mL of both bottoms
and distillate were recovered. All samples of bottoms and
distillate were analysed to determine the content of soaps and free
fatty acids using AOCS methods Cc 17-95 and Ca 5a-40
respectively.
[0081] Some samples of column bottoms were noted to have elevated
levels of free fatty acids. These samples were treated by briefly
contacting with a mixture of 1 molar potassium hydroxide dissolved
in glycerol to convert the fatty acids to soaps. The glycerol phase
was easily separated from the oil phase by decanting. Following
alkaline glycerol treatment silica (0.25% w/w Trisyl 600) and was
added to the oil phase and the phase was filtered over a bed of
celite.
Example 4:
Refining and Distillation of Tallow Methyl Ester
[0082] Tallow esters were refined and distilled as described for
rapeseed esters in Example 3.
Example 5:
Lubricity Testing of Methyl Canola and Tallow Esters
[0083] Lubricity was measured using a Munson Roller On Cylinder
Lubricity Evaluator (M-ROCLE; Munson, J. W., Hertz, P. B., Dalai,
A. K. and Reaney, M. J. T. Lubricity survey of low-level biodiesel
fuel additives using the "Munson ROCLE" bench test, SAE paper
1999-01-3590). The M-ROCLE test apparatus conditions are given in
Table1. M-ROCLE operation and equations used to describe lubricity
number are described above. Table 2 describes the samples subjected
to analysis.
[0084] Lubricity testing was performed on the first distillate and
column bottoms, which constituted about a four-fold concentrate of
high boiling substances. A total of 6 replications were performed
to allow for statistical analysis. All tests were performed on a 1%
solution of concentrate or distillate in kerosene. Table 3 contains
the results of analyses.
[0085] In testing it was found that kerosene produced the lowest
lubricity number and that all treatments increased lubricity number
with respect to controls. Among the treated samples the
concentrates consistently demonstrated the highest lubricity
numbers. The lubricity numbers for concentrates of canola and the
two tallow samples were not significantly different from each other
and in all cases the concentrates had greater lubricity than the
distillates. The lubricity numbers noted for the distillates were
lower than the concentrates, though higher than controls,
indicating that only half of the improvement in lubricity number
was contributed by the distilled methyl ester. In the two tallow
samples it was found that prior to distillation the lubricity
number was similar to the lubricity number for the concentrate.
[0086] Uniformly it was found that all treatments also decreased
wear scar area. Surprisingly it was found that although distilled
methyl esters significantly decreased wear scar area concentrates
produced the lowest wear scar areas. For example, tallow 1 methyl
ester (sample number 4) produced a wear scar area of 0.2410
mm.sup.2 while the distillate and concentrate of this sample
produced wear scars of 0.2763 mm.sup.2 and 0.2446 mm.sup.2
respectively (Table 3).
[0087] It was discovered that the treatments had little impact on
the coefficient of friction in the current test. TABLE-US-00002
TABLE 2 Description of refining and distillation conditions used to
prepare lubricity enhanced concentrates All additive samples were
Trisyl treated and Celite Filtered Methyl Esters Bottle Base
Material Fatty Bottle Sample # for Methyl Ester Acid % Wt. gr. #1
Canola Oil 0.04% 104 #2 Canola Oil 0.07% 105 Distillate #3 Canola
Oil 0.07% 84 Concentrate #4 Tallow 1 0.07% 93 #5 Tallow 1 0.07% 96
Distillate #6 Tallow 1 0.10% 90 Concentrate #7 Tallow 2 0.03% 88 #8
Tallow 2 0.06% 84 Distillate #9 Tallow 2 0.07% 98 Concentrate
[0088] TABLE-US-00003 TABLE 3 Wear Scar Lubricity Area Standard
Coefficient Sample Number Standard (mm{circumflex over ( )}2)
Deviation of Friction Standard number* (n = 6) Deviation (n = 6)
[mm{circumflex over ( )}2] (n = 6) Deviation Kerosene 0.7547 0.0778
0.3195 0.0238 0.1142 0.0050 #1 0.8620 0.0579 0.2907 0.0029 0.1210
0.0034 #2 0.8341 0.0484 0.2783 0.0183 0.1095 0.0017 #3 0.9464
0.0706 0.2557 0.0121 0.1180 0.0022 #4 0.9561 0.0552 0.2410 0.0222
0.1136 0.0022 #5 0.8373 0.0352 0.2763 0.0120 0.1189 0.0020 #6
0.9625 0.0456 0.2446 0.0102 0.1183 0.0019 #7 0.9348 0.0438 0.2623
0.0113 0.1163 0.0023 #8 0.8513 0.0492 0.2723 0.0092 0.1116 0.0013
#9 0.9555 0.0712 0.2547 0.0162 0.1182 0.0009 *number corresponds to
sample number in table 2
Example 6
Impact of Oil Extraction and Refining Procedures on the Lubricity
of Canola Oil
[0089] Approximately twenty kg (20.8) of canola seed was crushed in
a Komet expeller press through a 6 mm die face producing 7.9 kg of
oil with fines and 12.8 kg of meal. The oil was clarified by
passing over glass wool followed by centrifugation at 2000.times.g
for 15 min in a swing out rotor. The mass of the clarified oil was
7.2 kg. This oil was identified as pressed and unrefined or P-0.
The meal arising from pressing was extracted with hexane in 1.4 kg
batches in a soxhlet extractor. The hexane was collected and
evaporated in a rotary evaporator producing 1.5 kg of solvent
extracted oil. This oil is identified as solvent extracted and
unrefined or S-0. The combined oil yield from the two processes was
42% of the original seed mass. The two samples of oil were used for
further processing and analysis. Blending the crushed and solvent
extracted oils at a ratio of 5:1 produced the third sample. This
oil is identified as pressed, solvent extracted and unrefined or
PS-0.
[0090] All oil samples were analyzed to determine the level of
sterols (NMR), free fatty acids (AOCS Ca 5a-40), minerals (ICP) and
lubricity (Munson ROCLE).
[0091] Oils (P-0, S-0 and PS-0) were degummed by adding 0.2% by
weight of fifty percent citric acid to the oil while heating to
40-45.degree. C. for 30 minutes with agitation. After reaction with
the acid an additional of 2% of water (w/w) was added. The water
treated oils were then heated to 60-70.degree. C. for a further 20
minutes then centrifuged (2,000.times.g for 15 minutes). The upper
layer of clear oil was recovered and analyzed to determine FFA,
minerals and lubricity. Degumming produced three oil products:
pressed degummed oil, P-1; solvent extracted degummed oil, S-1; and
pressed and solvent extracted degummed oil PS-1
[0092] Approximately 300 g of each oil (P-1, S-1 and PS-1) was
neutralized or alkali refined, for further analyses and processing.
Alkali refining was achieved by adding a solution of 10% (w/w)
sodium hydroxide to the degummed oil. The free fatty acid level was
used to determine the stoichiometric amount of sodium hydroxide
solution required for neutralization with a small excess.
Neutralization was accomplished at 60-70.degree. C. with a reaction
time of 5 minutes with agitation. After neutralization the oil and
soap water solution were separated by centrifugation (2,000.times.g
for 15 minutes). The oil had a cloudy appearance. Evaporation of
the cloudy oil produced clear oil that was analyzed for FFA,
minerals and lubricity. Neutralization produced three oil products:
Pressed neutralized oil, P-2; solvent extracted neutralized oil,
S-2; and pressed and solvent extracted neutralized oil PS-2.
[0093] The alkali refined, neutralized oils (P-2, S-2 and PS-2)
were bleached by the addition of 1% (w/w) bleaching clay to oil
that had been preheated to 110.degree. C. under vacuum. The oil was
agitated in the presence of the bleaching clay for 30 min after
which the temperature was allowed to fall to 60.degree. C. prior to
release of the vacuum. The oil and clay were then filtered through
a bed of celite and Whatman No. 1 filter paper in a Buchner funnel.
The filtered oil was analyzed to determine FFA, minerals and
lubricity. Bleaching produced three oil products: Pressed bleached
oil, P-3; solvent extracted bleached oil, S-3; and pressed and
solvent extracted bleached oil PS-3.
[0094] In the final stage of processing the oils (P-3, S-3 and
PS-3) were deodorized by passage through a 2.0 inch diameter Pope
wiped film still. The still was adjusted to deliver oil at 2
mL/min, evaporation temperature was 170.degree. C. and vacuum was
10.sup.-2 mbar. Deodorizing produced three oil products: Pressed
deodorized oil, P-4; solvent extracted deodorized oil, S-3; and
pressed and solvent extracted deodorized oil PS-3.
[0095] Sterol is observed as a peak at 0.66 ppm in the proton
spectrum. The peak is small but may be quantified with a
sufficiently powerful spectrometer. The level of sterol in the
solvent extracted portion of the oil is approximately the level
found in the pressed oil (Table 4). With the exception of
deodorizing treatments none of the refining steps affected the
measured level of sterol.
[0096] Nine different mineral elements are observed in the ICP data
including silicon, sodium, potassium, iron, boron, phosphorous,
zinc, calcium, and magnesium. The amounts of most minerals are
higher in solvent extracted oils than the pressed oil. Refining
tends to remove minerals but its effect is different among the
three samples. Degumming reduced the phosphorous content of pressed
oil from 8 to 4 ppm (P-0 vs P-1) and from 168 to 57 ppm in the
mixed oil (PS-0 vs. PS-1) but had no effect on the level of
phosphorous (1030 ppm) in the solvent extracted oil (S-0 vs. S-1).
Upon completion of all refining steps the pressed oil was virtually
devoid of all mineral contamination showing only traces of tin (1
ppm, probably spurious) and silicon (7 ppm). Refining similarly
improved the quality of the mixed oil (PS-4) where only traces of
silicon, phosphorous, calcium and magnesium (3,2,2 and 2 ppm
respectively) were observed. Full refining was not useful in
removing materials from the solvent extracted oil where silicon,
sodium, phosphorous, calcium and magnesium were observed at
appreciable levels (10, 41, 197, 225 and 69 ppm respectively).
Trace levels of potassium and lead were reported but the latter
measurement was likely spurious instrument noise.
[0097] The effect of the three oils at all stages of refining on
kerosene lubricity was evaluated by preparing a 1% (w/w) solution
in kerosene and testing in a Munson Roller On Cylinder Lubricity
Evaluator to determine the coefficient of friction and wear scar
area. Lubricity number (LN) was calculated from the two numbers.
Wear scar area was greatly reduced by all treatments. Several
differences were observed among treatments but generally the size
of differences among treatments was much smaller than the
difference between untreated kerosene and the individual
treatments. Wear scar area was for all three unrefined oils from
all treatments. Degumming resulted in oils that produced a larger
wear scar. Other refining treatments did not affect wear scar
significantly.
[0098] All treatments lowered the coefficient of friction but
substantial differences among treatments were observed. Alkali
refined oils that had a greater coefficient of friction in all
cases while bleaching reduced friction coefficients only for
solvent extracted oil (S and PS, Table 4). Deodorizing also
increased the coefficient of friction for the two solvent extracted
oils. On average the coefficient of friction was lowest in oils
containing the solvent extracted components.
[0099] Lubricity number reflects the effect of the oil on both wear
scar and coefficient of friction. All oils regardless of the
treatment increase the lubricity number. The solvent extracted oil
provided the greatest increase in lubricity number over the blended
and pressed oil types. Refining does not appear to affect the LN of
pressed oil while it does result in interesting changes in the LN
of the solvent extracted fractions. In the solvent extracted oils
it is seen that degumming the oil lowers LN. Alkali refining has
little additional affect on LN but bleaching appears to restore the
LN though not to the levels observed in unrefined oil. Deodorizing
lowers LN in the solvent extracted and the blend oils.
TABLE-US-00004 TABLE 4 Effect of oil refining on select metal
component concentrations and lubricity factors wear Si Na K B P Zn
Ca Mg Sterol scar FFA (%) (PPM) (PPM) (PPM) (PPM) (PPM) (PPM) (PPM)
(PPM) (NMR) (.cndot.M.sup.2) C of F* LN P**-0*** 1.244 0 0 1 1 8 1
12 3 0.024 0.2634 0.1270 0.8193 P-1 1.231 1 1 0 3 4 0 1 1 0.021
0.2732 0.1179 0.8507 P-2 0.084 1 7 0 2 1 0 0 0 0.022 0.2830 0.1239
0.7800 P-3 0.070 1 0 0 1 0 0 0 0 0.021 0.2689 0.1222 0.8359 P-4
0.056 7 0 0 0 0 0 0 0 0.018 0.2754 0.1218 0.8167 PS-0 1.866 2 1 32
1 168 1 70 33 0.240 0.2519 0.1143 0.9543 PS-1 1.840 2 1 8 2 57 0 20
9 0.011 0.2944 0.1092 0.8527 PS-2 0.141 1 2 0 1 5 0 4 0 0.027
0.2877 0.1233 0.7722 PS-3 0.126 1 0 0 0 3 0 2 1 0.023 0.2716 0.1143
0.8844 PS-4 0.084 3 0 0 0 2 0 2 2 0.007 0.2870 0.1171 0.8146 S-0
4.573 10 8 209 1 1030 3 368 190 0.040 0.2365 0.1127 1.0318 S-1
5.434 12 10 207 3 1040 3 378 190 0.042 0.2658 0.1143 0.9006 S-2
0.310 10 45 4 1 207 0 273 74 0.034 0.2504 0.1228 0.8960 S-3 0.364
10 42 3 1 199 0 255 71 0.035 0.2601 0.1082 0.9738 S-4 0.364 10 41 3
0 197 0 255 69 0.033 0.2578 0.1241 0.8559 *Coefficient of friction
**P = pressed oil, PS = pressed and solvent extracted oil S =
solvent extracted oil ***0 = unrefined, 1 = Degummed, 2 = Degummed
and neutralized, 3 = Degummed, neutralized and bleached, 4 =
Degummed, neutralized, bleached and deodorized.
Example 7:
Influence of Canola Oil Additization on Wear and Fuel Economy
[0100] This example describes the canola lubricity field
performance of a fully wear documented gasoline engine, a 3.0 L V6
Toyota Camry. Tests began with an additization rate of 250 ppm
Canola Oil in unleaded commercial gasoline under summer driving
conditions. To reference these tests a control summer test of
10,000 km was conducted without the canola oil present. The same
motor oil Pennzoil SJ SAE 10W-30 was used through out the reference
and treatment test periods. Eight oil samples were taken. Data was
analyzed in two parts, 0 to 5,800 km and 5,800 km to 10,510 km. The
driving was 65% highway and 35% city. Starts totaled 458 Cold and
327 Hot. Ambient temperatures ranged from a mean minimum of
8.5.degree. C. to a maximum of 20.8.degree. C. Table 5 shows the
comparison of net wear iron ppm levels generated up to the 6,000
summer distances with regular gasoline and with 250 ppm canola oil
additization.
[0101] Canola oil supplemented gasoline produced a significant ICP
wear reduction compared with the control. The overall averaged wear
rate with regular gasoline was 0.99 ppm Fe/1,000 km while the
instantaneous method yielded a rate of 0.87 ppm Fe/1,000 km for the
reference fuel. The reference results exceeded the 0.63-0.66 ppm
Fe/1,000 km obtained with canola oil present and revealed that
canola oil additized fuel had resulted in a 33% wear reduction
overall and a 26% reduction instantaneously. The average mileage
obtained with canola oil present was 28.1 MPG while reference gas
mileage was 4% better at 29.3 MPG. In this test canola oil
additization lowered fuel economy.
[0102] In Table 6 the ferrography for reference gasoline revealed a
wear particle density of 15 with other contaminants counting 8. The
canola oil additized fuel run analysis indicated 14 for wear
particles and 8 for other debris, indicating no effect of the
treated fuel on larger ferrographic particles.
[0103] The filter analysis with 250 ppm canola oil additized fuel
reveals rust, dirt, and varnish particles. The largest translucent
particles of varnish measure about 200 .mu.m. The spectrographic
analysis of the filter residues indicated silicon, iron, copper
traces and sodium. The presence and level of the contaminants is
normal.
[0104] Both neutralization numbers were not affected significantly
by canola oil treatment. Motor oil taken from the vehicle after
operation on 250 ppm canola oil additized fuel lowered the total
base number to 6.06 while the total acid number remained at 3.66
(Table 6).
[0105] After summer operation on gasoline containing 250 ppm canola
oil (6,261 km) viscosity was lowered to 57.6 cSt at 40.degree. C.
and 8.95 cSt at 100.degree. C. This represented a 17% drop in
viscosity at 40.degree. C. and an 18% change at 100.degree. C. Also
the presence of 1% fuel dilution of the oil was indicated after
driving 10,243 km, when the oil was changed.
Example 8:
Influence of Canola Methyl Ester Additization on Wear and Fuel
Economy
[0106] This example describes the Canola lubricity field
performance of a fully wear documented gasoline engine, a 3.0L V6
Toyota Camry. Tests began with an additization rate of 125 ppm
canola oil methyl ester (CME) in unleaded commercial gasoline under
summer driving conditions. To reference these tests a control
summer test of 10,000 km was conducted without the canola methyl
ester present. The same motor oil Pennzoil SJ SAE 10W-30 was used
through out the reference and treatment test periods. For canola
methyl ester additization tests a distance of 10,017 km was covered
with 74% highway driving. Cold starts added up to 278 while hot
starts equaled 311. Temperature means ranged from 12.3.degree.C. to
25.4.degree. C.
[0107] The ICP iron wear rates were remarkably low with the 125 ppm
CME treatment (Table 5). The overall rate method yielded only 0.50
ppm Fe/1,000 km while the instant point-to-point mean was similar
at 0.48 ppm Fe/1,000 km. This lower CME treatment resulted in 49%
to 45% wear reduction compared to the unadditized reference. It is
clearly illustrated that CME wear performance is superior to both
the reference and the 250 ppm canola oil additized fuel
performance. Both canola additives are considerably better than the
reference regular gasoline. The calculated mean fuel economy with
125 ppm CME was some 5% better than for the reference gasoline,
yielding 30.8 MPG compared to the former 29.3 miles per Imperial
gallon on regular gasoline.
[0108] The consistency of the reference wear readings were
established by comparing average ICP data wear rates (Table 5) for
regular gasoline. These averages were 0.87, 0.85, 0.99 and 0.87 ppm
Fe/1,000 km. On the basis of this long-term reference, the listed
per-cent summer wear rate reductions were 33% and 28% for
instantaneous and cumulative wear when operating on 125 ppm
CME.
[0109] Ferrography analysis of motor oil obtained after operation
on 125 ppm CME totaled 6 wear particles and 2 other particles. This
represents a reduction of 60% and 87% reduction from reference
analysis. Most of these wear metals were described in the
ferrography reports as "low alloy steel showing rubbing/sliding
wear" although it is difficult to distinguish between very small
steel and cast-iron particles, originating from the cylinder
block.
[0110] The last filter obtained after operation on 125 ppm CME had
far less debris in it compared to the other two filters. The white
filter paper support shows through the particles, which are at a
much lower concentration. Dirt/dust, rust and varnish are the major
contaminants. The presence of silicon, iron, and traces of lead,
copper and tin appeared spectrographically.
[0111] Operation on the CME additized fuel lowered the TBN to 6.19
while the TAN climbed to 4.20. This revealed that both
neutralization numbers were not affected significantly by the
Canola methyl ester.
[0112] Viscosity of the motor oil was also determined after
operation on 125 ppm CME. After the 10,016 km ended, the oil tested
59.4 at 40.degree. C., a 13% drop. For 100.degree. C. the values
9.43 cSt were reported, with a 14% drop. Viscosity performance was
within specifications
[0113] With 125 ppm Canola Methyl Ester added to the gasoline
engine wear rate was reduced by almost one-half, to only 0.5 ppm
Fe/1,000 km, potentially doubling engine life. Field fuel economy
rose by 5%. The engine oil remained within neutralization and
viscosity specifications after some 10,000 km of field-testing. The
ferrographic and oil filter debris levels were markedly reduced and
appeared normal. Furthermore no driveability or other engine
performance problems were detected as the result of the specific
CME treatment rate used in unleaded regular gasoline.
Example 9:
Winter Canola Oil Gasoline Field Testing, Wear and Fuel Economy
[0114] This example describes the Canola lubricity field
performance of a fully wear documented gasoline engine, a 3.0 L V6
Toyota Camry. Tests began with an additization rate of 250 ppm
canola oil in unleaded commercial gasoline under winter driving
conditions. To reference these tests a series of winter reference
runs were performed without the additive. The same motor oil
Pennzoil SJ SAE 10W-30 was used through out the reference and
treatment test periods.
[0115] The reference wear rate data is recorded in Table 5
reflecting the accumulation of iron (ppmFe/1,000 km value) averaged
2.24 (overall) and 1.91 (measuring point to point). Reference
gasoline economy records averaged 24.5 MPG. The numbers of cold and
hot starts during the winter reference period were recorded. Mean
ambient winter temperatures were in the -15.degree. C. to
-7.degree. C. range. The proportion of highway driving was
calculated as 71% and 43% for the reference tests.
[0116] The canola oil additive was pre-mixed with 50% gasoline to
facilitate tank blending upon cold refueling. The canola oil test
data involved 224 cold and 101 hot starts with 72% highway driving.
The fuel economy rose to 27.5 MPG, a 12% improvement in referenced
shorter-term mileage. Table 5 compares regular gasoline and the 250
ppm canola oil additive. Calculations in Table 5 indicated that
wear rates decreased slightly with 250 ppm canola oil additized
fuel, to 2.02 and 1.73 ppm Fe/1,000 km. These reductions in wear
were 6% and 20% based on the long-term reference and 10% and 9%
based on the shorter-term comparative regular gas references.
[0117] For the canola oil additized fuel treatment, the level of
ferrographic wear particles reached "12" while contaminants
remained at "7". This represented 11% lower wear particle count
than previously referenced. The magnetic iron trend remained very
low and unchanged at 0.2 .mu.g/mL.
[0118] The oil filter taken after operation on 250 ppm canola oil
additized fuel revealed contaminants as dirt, rust and varnish. The
spectrographic analysis revealed iron, silicon, and traces of
sodium, copper, and potassium in the filter debris. Filter analysis
results were normal.
[0119] The winter 250 ppm canola oil fuel additive resulted in a
5.8 TBN and a 2.5 TAN indication. This 5.8 reading revealed a
similar drop in reserve alkalinity for TBN, noting the 5.7 TBN for
the reference fuel. The TAN of 2.5 for canola oil additized fuel
treatment had not varied significantly from the 2.5 value for new
oil or the 2.7 value for oil after operation on the reference
fuel.
[0120] Motor oil obtained after operation on 250 ppm canola oil
additized fuel under winter operation conditions had viscosity of
48.5 cSt at 40.degree. C. and 8.73 cSt at 100.degree. C. The
viscosity had decreased 21% at 40.degree. C. and 17% drop at
100.degree. C. from new oil. Compared to regular fuel, the relative
additional loss of viscosity was 5% at 40.degree. C. and 4% at
100.degree. C. for the canola oil additized gasoline.
[0121] The winter tests with 250 ppm canola methyl ester added to
the gasoline were encouraging. Engine wear rate was reduced by
almost one-half, to only 0.5 ppm Fe/1,000 km, potentially doubling
engine life. Field fuel economy rose by 5%. The engine oil remained
within neutralization and viscosity specifications after some
10,000 km of field-testing. The ferrographic and oil filter debris
levels were markedly reduced and appeared normal. Furthermore no
driveability or other engine performance problems were detected as
the result of the specific CME treatment rate used in unleaded
regular gasoline.
Example 10:
Winter Canola Methyl Ester Gasoline Field Testing, Wear and Fuel
Economy
[0122] This example describes the Canola lubricity field
performance of a fully wear documented gasoline engine, a 3.0L V6
Toyota Camry. Tests began with an additization rate of 250 ppm
canola methyl ester in unleaded commercial gasoline under winter
driving conditions. To reference these tests a series of winter
reference runs were performed without the additive. The same motor
oil Pennzoil SJ SAE 10W-30 was used through out the reference and
treatment test periods.
[0123] The reference wear rate data is recorded in Table 5
reflecting the accumulation of iron (ppmFe/1,000 km value) averaged
2.24 (overall) and 1.91 (measuring point to point). Reference
gasoline economy records averaged 24.5 MPG. The numbers of cold and
hot starts during the winter reference period were recorded. Mean
ambient winter temperatures were -7.9.degree. C. and -3.7.degree.
C. the daily averaged minimum and maximums. The proportion of
highway driving was calculated as 71% and 43% for the reference
tests.
[0124] The canola methyl ester tests spanned 4,202 km with 106 cold
and 113 hot starts logged with 72% highway driving. The average
fuel economy during this test was 27.0 MPG, some 10% better
compared to the regular gas references. Table 5 compares the net
wear iron in the two winter test runs. The gasoline alone graph
climbs higher than with 250 ppm the canola methyl ester supplement.
The engine-wear iron spectrometry calculations revealed rates of
1.55 and 1.27 ppm Fe/1,000 km with canola methyl ester. These were
28% and 41% lower than the long-term references and 31% and 41%
below the shorter-term gasoline references as shown in Table 5. No
driveability problems were experienced, with good power, starting,
and stable idling rpm demonstrated while using 250 ppm canola
methyl ester as a gasoline additive.
[0125] With the canola methyl ester additive, ferrography indicated
wear particles were at the "13" level while a ranking of "8"
appeared for contaminants. Most metal particles are low alloy steel
showing rubbing/sliding. Traces of copper/copper alloy (up to 40
microns) present were comments. The magnetic iron trend stayed
minimally the same at 0.2 .mu.g/mL.
[0126] Analysis of the oil filter after operation on 250 ppm canola
methyl ester in winter conditions indicated that contaminants were
dirt, dust, rust and varnish. The debris texture looked fine with
some metallic reflections. Spectrographic analysis revealed
silicon, iron, and traces of sodium, potassium, copper and tin in
the residue. These filter results were also judged normal.
[0127] Oil viscosity from oil taken after operation on canola
methyl ester for 4,104 km was 51.9 cSt at 40.degree. C. and 9.46 at
100.degree. C. No fuel dilution of the motor oil was observed
during the trial. These test values represented similar viscosity
to that obtained after similar operation on reference gasoline. The
250 ppm canola methyl ester treatment under winter conditions
appeared better in terms of viscosity dilution than the 250 ppm
canola oil additive.
Example 11
[0128] Twenty liters of methyl esters were prepared according to
example 1 using canola oil obtained at a local grocery. The esters
were then placed in 2 L lots in a high vacuum vessel used to feed a
2'' wiped film evaporator (Pope Scientific, Saukville WI). Vacuum
(0.01 torr) was applied to the high vacuum flask to remove residual
volatile materials. After vigorous bubbling had ceased the material
was passed through the wiped film still at an initial high rate (20
mL/min) to remove low-boiling materials. The walls of the still
were heated to 80 C for this process. During evaporation vapors
were condensed by traps chilled with liquid nitrogen. After
removing removing volatiles from the methyl ester solution the
still was heated to 170 C and the methyl esters were re introduced
and the vacuum was maintained. The flow of liquid was adjusted so
that the flow of distillate was approximately 20 times the flow of
residue. During this time 1.5 L of residue was collected. The
undistilled residue was introduced to the still and after
distillation under the same conditions a concentrate of 300 mL was
obtained.
[0129] Analysis of the methyl esters and the canola oil with high
field proton NMR Spectroscopy (500 MHz Bruker, Milton, ON Canada)
revealed a small but observable peak in the spectrum contributed by
plant sterols at 0.67 ppm. The distillate did not have observable
sterol peaks. Addition of pure sterol (cholesterol or cholestanol)
to the distillate restored the peak. The residue of the
distillation was also observed using high-field proton NMR. The
proton spectrum was comparable to a mixture of plant free and bound
sterols with small amount of residual of methyl esters. With
further preparation steps known to those skilled in the art, the
free and bound sterol fraction may be separated and used as
components of nutritional concentrates.
Example 12
Production of Safflower Oil Ethyl Esters
[0130] Potassium hydroxide pellets (100 g) were dissolved in a 4 L
beaker containing 3500 g of absolute ethanol. The caustic ethanol
solution was added to ten kg of safflower oil in a 20 L plastic
pail held at room temperature and the mixture was stirred for 2
hours at room temperature. After 2 hours the solution was allowed
to settle for 24 hours and the clear upper layer of ethyl esters
was decanted into a clean plastic 20 L pail. The lower layer was
transferred to a 4 L separatory funnel and the lower layer of
glycerin was separated from the remaining upper layer of ethyl
esters. The recovered ethyl esters were combined with the decanted
esters. The ethyl esters were then washed by the addition of 200 g
of water and vigorous agitation of the solution. The water was
allowed to settle and the methyl ester layer was again decanted
into a clean plastic pail. The lower water layer was transferred to
a 2 L separatory funnel and allowed to settle for 4 hours. The
lower water layer was drained and the upper layer of washed methyl
esters was combined with the decanted washed esters. The washed
esters were placed in a 20 L rotary evaporator and all water and
ethanol was removed by evaporation for 2 hours at 80 C. The dried
ester layer had a slightly cloudy appearance.
[0131] Celite (250 g) was mixed with a one liter portion of the
cloudy ester layer. The slurry was then used to form a filtration
bed in a 20 cm clean and oven dry ceramic Buchner funnel. The first
sample of ester was returned to the top of the filter bed.
Thereafter the remaining volume of ethyl esters was passed over the
filter bed to remove particulate matter. Proton NMR and analysis of
the fatty acid esters using gas chromatography indicated that the
clear solution was greater than 95% fatty acid ethyl esters.
Example 13
Wiped Film Distillation of Safflower Oil Ethyl Esters
[0132] Ten liters of fatty acid ethyl esters were prepared
according to example 12 using safflower oil obtained at a local
grocery. The esters were then placed in 2 L lots in a high vacuum
vessel used to feed a 2'' wiped film evaporator (Pope Scientific,
Saukville Wis.). Vacuum (0.01 torr) was applied to the high vacuum
flask to remove residual volatile materials. After vigorous
bubbling had ceased the material was passed through the wiped film
still at an initial high rate (20 mL/min) to remove low-boiling
materials. The walls of the still were heated to 80 C for this
process. During evaporation vapors were condensed by traps chilled
with liquid nitrogen. After removing removing volatiles from the
methyl ester solution the still was heated to 140 C and the ethyl
esters were re introduced and the vacuum was maintained. The flow
of liquid was adjusted so that the flow of distillate was
approximately 10 times the flow of residue. During this time 1 L of
residue was collected. The residue of distillation was introduced
to the still and after distillation under the same conditions a
concentrate of 50 mL was obtained.
[0133] Analysis of the ethyl esters and the safflower oil with high
field proton NMR Spectroscopy (500 MHz Bruker, Milton, ON Canada)
revealed two small but observable peaks in the spectrum contributed
by plant sterols and other triterpene alcohols. The distillate did
not have observable sterol peaks. The residue of the distillation
was also observed using high-field proton NMR. The proton spectrum
was comparable to a mixture of ethyl esters with plant free and
bound sterols and triterpene alcohols. With further preparation
steps known to those skilled in the art the free and bound sterol
fraction may be separated and used as components of nutritional
concentrates. The preparation may also be used as a direct source
of sterols.
Example 14:
Two Stage Transesterification of Canola Oil with Methanol and
Potassium Hydroxide
[0134] Methyl esters of canola oil, also known to those skilled in
the art as low erucic acid rapeseed oil, were prepared using a
two-stage base catalysed transesterification. The two-stage
reaction was required to remove glyceride from the final product.
Prior to the reaction the catalyst was prepared by dissolving
potassium hydroxide (190 g) in methanol (3800 g). The catalyst
solution was divided into two 1995 g fractions and one fraction was
added to 20 L of canola oil (purchased from a local grocery store)
in a 30 L stainless steel pot. The oil, catalyst and methanol were
covered and stirred vigorously for 1 hour with an overhead stirrer.
After stirring, the products of the reaction were allowed to settle
for 2 hours. At this time a cloudy upper layer and a viscous lower
layer had separated. The majority of the upper layer was decanted
and the remaining layers were separated using a seperatory funnel.
The upper layers were pooled, returned to the stainless pot with
overhead stirrer and the remaining potassium hydroxide in methanol
solution was added. This second mixture was stirred vigorously in a
covered beaker for 1 hour and allowed to settle overnight. The
mixture settled to form two layers. The upper layer was collected
by decanting and using a separatory funnel.
[0135] After separation of phases the upper layer was mixed with
400 mL of water. The water was removed from the upper phase by
decanting. The washed esters were placed in a 20 L rotary
evaporator and all water and ethanol was removed by evaporation for
2 hours at 80 C. The resulting esters had a slightly cloudy
appearance.
[0136] Celite (250 g) was mixed with a one liter portion of the
cloudy ester layer. The slurry was then used to form a filtration
bed in a 20 cm clean and oven dry ceramic Buchner funnel. The first
sample of ester was returned to the top of the filter bed.
Thereafter the remaining volume of methyl esters was passed over
the filter bed to remove particulate matter. Proton NMR and
analysis of the fatty acid esters using gas chromatography
indicated that the clear solution was greater than 95% fatty acid
methyl esters.
Example 15
Preparation of a Nutritional Concentrate From Transesterified
Canola Oil and Analysis of a Potential Biologically Active
Concentrate.
[0137] Twenty liters of methyl esters were prepared according to
example 14 using canola oil obtained at a local grocery. The esters
were then placed in 2 L lots in a high vacuum vessel used to feed a
2'' wiped film evaporator (Pope Scientific, Saukville Wis.). Vacuum
(0.01 torr) was applied to the high vacuum flask to remove residual
volatile materials. After vigorous bubbling had ceased the material
was passed through the wiped film still at an initial high rate (20
mL/min) to remove low-boiling materials. The walls of the still
were heated to 80 C for this process. During evaporation vapors
were condensed by traps chilled with liquid nitrogen.
[0138] The still was then heated to 170 C and the methyl esters
were re introduced and the vacuum was maintained. The flow of
liquid was adjusted so that the flow of distillate was
approximately 20 times the flow of residue. During this time 1.5 L
of residue was collected. The undistilled residue was introduced to
the still and after distillation under the same conditions a
concentrate of 300 mL was obtained.
[0139] Analysis of the methyl esters and the canola oil with high
field proton NMR Spectroscopy (500 MHz Bruker, Milton, ON Canada)
revealed a small but observable peak in the spectrum contributed by
plant sterols at 0.67 ppm. The distillate did not have observable
sterol peaks. Addition of pure sterol (cholesterol or cholestanol)
to the distillate restored the peak. The residue of the
distillation was also observed using high-field proton NMR. The
proton spectrum was comparable to a mixture of of plant free and
bound sterols with small amount of residual of methyl esters. With
further preparation steps known to those skilled in the art the
free and bound sterol fraction may be separated and used as
components of nutritional concentrates.
Example 16
Transesterification of Safflower Oil with Ethanol.
[0140] Potassium hydroxide pellets (100 g) were dissolved in a 4 L
beaker containing 3500 g of absolute ethanol. The caustic ethanol
solution was added to ten kg of safflower oil in a 20 L plastic
pail held at room temperature and the mixture was stirred for 2
hours at room temperature. After 2 hours the solution was allowed
to settle for 24 hours and the clear upper layer of ethyl esters
was decanted into a clean plastic 20 L pail. The lower layer was
transferred to a 4 L separatory funnel and the lower layer of
glycerin was separated from the remaining upper layer of ethyl
esters. The recovered ethyl esters were combined with the decanted
esters. The ethyl esters were then washed by the addition of 200 g
of water and vigorous agitation of the solution. The water was
allowed to settle and the methyl ester layer was again decanted
into a clean plastic pail. The lower water layer was transferred to
a 2 L separatory funnel and allowed to settle for 4 hours. The
lower water layer was drained and the upper layer of washed methyl
esters was combined with the decanted washed esters. The washed
esters were placed in a 20 L rotary evaporator and all water and
ethanol was removed by evaporation for 2 hours at 80 C. The dried
ester layer had a slightly cloudy appearance.
[0141] Celite (250 g) was mixed with a one liter portion of the
cloudy ester layer. The slurry was then used to form a filtration
bed in a 20 cm clean and oven dry ceramic Buchner funnel. The first
sample of ester was returned to the top of the filter bed.
Thereafter the remaining volume of ethyl esters was passed over the
filter bed to remove particulate matter. Proton NMR and analysis of
the fatty acid esters using gas chromatography indicated that the
clear solution was greater than 95% fatty acid ethyl esters.
Example 17
Preparation of a Nutritional Concentrate from Transesterified
Safflower Oil and Analysis of a Potential Nutritional
Concentrate.
[0142] Ten liters of fatty acid ethyl esters were prepared
according to example 16 using safflower oil obtained at a local
grocery. The esters were then placed in 2 L lots in a high vacuum
vessel used to feed a 2'' wiped film evaporator (Pope Scientific,
Saukville Wis.). Vacuum (0.01 torr) was applied to the high vacuum
flask to remove residual volatile materials. After vigorous
bubbling had ceased the material was passed through the wiped film
still at an initial high rate (20 mL/min) to remove low-boiling
materials. The walls of the still were heated to 80 C for this
process. During evaporation vapors were condensed by traps chilled
with liquid nitrogen. After removing removing volatiles from the
methyl ester solution the still was heated to 140 C and the ethyl
esters were re introduced and the vacuum was maintained. The flow
of liquid was adjusted so that the flow of distillate was
approximately 10 times the flow of residue. During this time 1 L of
residue was collected. The residue of distillation was introduced
to the still and after distillation under the same conditions a
concentrate of 50 mL was obtained.
[0143] Analysis of the ethyl esters and the safflower oil with high
field proton NMR Spectroscopy (500 MHz Bruker, Milton, ON Canada)
revealed two small but observable peaks in the spectrum contributed
by plant sterols and other triterpene alcohols. The distillate did
not have observable sterol peaks. The residue of the distillation
was also observed using high-field proton NMR. The proton spectrum
was comparable to a mixture of ethyl esters with plant free and
bound sterols and triterpene alcohols. With further preparation
steps known to those skilled in the art the free and bound sterol
fraction may be separated and used as components of nutritional
concentrates. The preparation may also be used as a direct source
of sterols.
Example 18
Recovery of Non Esterified Sterols From Canola Methyl Ester
Distillate Residue
[0144] The residue of distillation obtained from Example 15 (0.50
g) was mixed with KOH (0.3 g) dissolved in ethanol (2.5 mL) and
water (2.5 mL) The mixture was heated at 65 C for 3 hours after
which the ethanol was removed under vacuum. The resulting residue
was diluted with water (15 mL) and the unsaponifiable matter was
extracted with petroleum ether (3.times.15 mL). The combined
organic phases were dried over anhydrous sodium sulphate.
Evaporation of the petroleum ether under reduced pressure gave a
white solid (158 mg). A portion of the solid was dissolved in
deuterated chloroform and placed in an NMR tube. Analysis of the
solid with high field proton NMR Spectroscopy (500 MHz Bruker,
Milton, ON Canada) revealed that the solid was primarily a mixture
of the free alcohol forms of phytosterol compounds.
Example 19
Separation of Fractions From the Canola Methyl Ester Distillate
Residue by Silica Chromatography
[0145] Fifteen grams of silica gel 60 was packed in a 10 cm glass
column and the column was washed with 50 mL of n-hexane. The wash
was discarded. Canola methyl ester distillate residue (0.4 g) was
dissolved in hexane and added to the column. The column was then
washed sequentially with 50 mL of n-hexane, 50 mL of 3% diethyl
ether in n-hexane, 50 mL of 10 percent ethyl acetate in n-hexane
and, finally, 50 mL of 25% ethyl acetate in n-hexane. The repeated
extractions produced four fractions with masses of 250 mg, 50 mg,
10 mg and 65 mg respectively after the complete removal of the
extraction solvent. The first three fractions were oil like in
nature while the last fraction was a white solid. Desolventized
samples were dissolved in deuterated chloroform and placed in NMR
tubes for analysis. Analysis of the fractions with high field
proton NMR Spectroscopy (500 MHz Bruker, Milton, ON Canada)
revealed that the fractions were 1) a mixture of sterol esters of
fatty acids with some fatty acid methyl ester; 2) a mixture of
fatty acid methyl esters with some sterol ester; 3) a complex
mixture containing Fatty acid esters as well as some unknown
compounds; 4) A highly enriched fraction of phytosterols in a free
alcohol form.
* * * * *