Note: Descriptions are shown in the official language in which they were submitted.
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A NEW BIOFUEL COMPOSITION
Field of the invention
[0001] The present invention relates to a new rapeseed
alkyl esters composition. The present invention further relates
to a process to obtain said new composition and its use as
biodiesel.
Background
[0002] For years, biodiesel has been considered as an
alternative to petroleum based diesel. Biodiesel is a general
term referring to a fuel comprised of mono-alkyl esters of long
chain fatty acids derived from vegetable oils or animal fats.
It can be used per se as fuel or as an additive, generally in a
blend with petroleum-based diesel fuel.
[0003] The numerous advantages of using Biodiesel are
well known. Indeed, it offers similar fuel economy, horsepower
and torque to petroleum diesel while providing superior
lubricity. Its use results in a substantial reduction of
emissions of unburned hydrocarbons, carbon monoxide, and
particulate matter. Moreover, it is essentially free of sulfur
and aromatics.
CONFIRMATION COPY
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[0004] Biodiesel is therefore regarded as a renewable,
non-toxic and.biodegradable fuel alternative or additive.
[0005] Nowadays biodiesel has to.satisfy very strict
specifications to insure proper performance. Indeed, the pure
biodiesel (B100) must meet a standard, through many specified
parameters, before being used as a pure fuel or being blended
with petrodiesel.
[0006] Some of these specifications refer to the
temperature properties of biodiesel, such as the flash point,
the cetane number, the cloud point, etc., some others refer to
its composition, such as glycerine content, water and sediment
content, sulphated ash content, phosphorus content, etc., and
some others measure the acid number, the kinematic viscosity,
etc.
{0007] Because of the current environmental and security
concerns, there have been many attempts to improve biodiesel
and/or the methods for its preparation.
[0008] But the main drawbacks with biodiesel products
remain their temperature properties and also their reactivity
toward oxidation and polymerization.
[0009] There is a high demand of a biofuel composition
which overcomes or mitigates the problems of prior art
biofuels.
[0010] The Australian document available on the internet
(http://www.biodiversity.ea.gov.au/atmosphere/biodiesel/pubs/pa
per.pdf), mentions new high oleic rapeseed varieties and also
new low linolenic varieties as potential varieties to be used
for biodiesel.
[0011] Nevertheless, having regard to the fatty acids
composition of an oil or fat used for the production of
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biodiesel, it is generally admitted that the more saturated
fatty acids, i.e. palmitic acid (16:0), and/or stearic acid
(18:0) that are present:
- the higher the biodiesel stability (oxidation stability,
thermal and storage stability);
- the lower the probability to form polymerised molecules
under high temperatures and pressure (e.g. when unburned traces
of biodiesel are washed down into the engine crankcase and
exposed to high stress levels caused by high temperature and
pressures);
- the higher the cetane-number for better engine performance.
[0012] It is also admitted that the presence of
linolenic acid methyl ester in biodiesel increases the rate of
biodiesel polymerisation adversely affecting engine
operability. But in the meantime, its total absence in oil
generates a drop of the cloud point or cold filter plugging
point ( CFPP ) .
Summary of the invention
[0013] The present invention is based on the surprising
discovery that the transesterification of rapeseed oil showing
low, or even very low, saturated fatty acids content may
nevertheless be advantageous, particularly when said oil
composition shows high or very high oleic acid content and/or
low or very low linolenic acid content.
[0014] The present invention provides a new Rapeseed
alkyl-ester(s) composition, said composition comprising less
than about 7%, 6,5%, 6% or 5,5%, preferably between about 7%
and about 5%, more preferably between about 7% and about 5,5%
of mono-alkyl-ester(s) of saturated fatty acids, based upon the
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total weight of the mono-alkyl-esters of fatty acids present in
the composition.
[0015] The present invention provides a new Rapeseed
alkyl-ester(s) composition, said composition comprising more
than about 72%, 75%, 80%, or 85%, preferably between about 70%
and about 85% of mono-alkyl-ester(s) of oleic acid, and less
than about 7%, 6,5%, 6% or 5,5%, preferably between about 7%
and about 5%, more preferably between about 7% and about 5,5%
of mono-alkyl-ester(s) of saturated fatty acids, based upon the
total weight of the mono-alkyl-esters of fatty acids present in
the composition.
[0016] Also provided is a new rapeseed alkyl-ester(s)
composition, which comprises less than about 4%, 3,5%, 3%, 2%,
or 1%, preferably between about 4% and about 1% of mono-alkyl-
ester(s) of linolenic acid and less than about 7%, 6,5%, 6% or
5,5%, preferably between about 7% and about 5%, more preferably
between about 7% and about 5,5% of mono-alkyl-ester(s) of
saturated fatty acids, based on the total weight of mono-alkyl-
esters of fatty acids in the composition.
[0017] The present invention also provides a new
rapeseed alkyl-ester(s) composition comprising more than about
72%, 75%, 80%, or 85%, preferably between about 70% and about
85% of mono-alkyl-ester(s) of oleic acid, less than about 40,
3,5%, 3%, 2%, 1,5% or 1%, preferably between about 4% and about
1% of mono-alkyl ester(s) of linolenic acid, and less than
about 7%, 6,5%, 6% or 5,5%, preferably between about 7% and
about 5%, more preferably between about 7% and about 5,5% of
mono-alkyl-ester(s) of saturated fatty acids, based on the
total weight of mono-alkyl-esters of fatty acids in the
composition.
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[0018] It is to be understood that any of the
compositions of the present invention comprises further fatty
acid esters that are characteristic of rapeseed oil.
[0019] Another object of the invention is a process for
5 preparing a composition of the present invention comprising the
transesterification step of a rapeseed oil comprising less than
about 7%, 6,5%, 6% or 5%, preferably between about 7% and about
5,5%, more preferably between about 7% and about 5,5% of
saturated fatty acids, based on the total weight of fatty acids
in the composition.
[0020] Another object of the invention is a process for
preparing a composition of the present invention comprising the
transesterification step of a rapeseed oil comprising at least
about 72%, 75%, 80%, or 85%, preferably between about 70% and
about 85% of oleic acid and less than about 7%, 6,50, 6% or
5,5%, preferably between about 7% and about 5%, more preferably
between about 7% and about 5,5% of saturated fatty acids, based
on the total weight of fatty acids in the composition.
[0021] Also provided is a process for preparing a
composition of the present invention comprising the
transesterification step of a rapeseed oil comprising at most
about 4%, 3,5%, 3%, 2%, 1,5% or 1%, preferably between about 4%
and about 1% of linolenic acid and less than about 7%, 6,5%, 6%
or 5,5%, preferably between about 7% and about 5%, more
preferably between about 7% and about 5,5% of saturated fatty
acids, based on the total weight of fatty acids in the
composition.
[0022] Another object of the present invention is the
use of a composition of the present invention in (diesel)
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engines, as biodiesel or as an additive in other compositions,
e.g. fuels.
Detailed description of the invention
[0023] The present invention relates to a new rapeseed
mono-alkyl ester(s) composition comprising less than about 7%,
6,5%, 6% or 5,5%, preferably between about 7% and about 5%,
more preferably between about 7% and about 5,50 of mono-alkyl
ester(s) of saturated fatty acids, based upon the total weight
of the mono-alkyl esters of fatty acids present in the
composition.
[0024] The present invention relates to a new rapeseed
mono-alkyl ester(s) composition comprising at least about 72%;
73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%,
85%, 86%, 87%, 88%, 89%, or 90% of mono-alkyl ester(s) of oleic
acid and less than about 7%, 6,50, 6% or 5,50 of mono-alkyl
ester(s) of saturated fatty acids, based upon the total weight
of the mono-alkyl esters of fatty acids present in the
composition.
[0025] The present invention also relates to a rapeseed
alkyl-ester(s) composition, which comprises less than about 4%,
3,5%, 3%, 2,5%, 2%, 1,5% or 1% of mono-alkyl esters of
linolenic acid and less than about 7%, 6,5%, 6% or 5,5% of
mono-alkyl ester(s) of saturated fatty acids, based on the
total weight of mono-alkyl esters of fatty acids in the
composition.
[0026] The present invention also relates to a new
rapeseed alkyl-ester(s) composition comprising more than about
72%; 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%,
84%, 85%, 86%, 87%, 88%, 89%, or 90% of mono-alkyl ester(s) of
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oleic acid, less than about 4%, 3,5%, 3%, 2,5%, 2%, 1,5% or 1%
of mono-alkyl ester(s) of linolenic acid, and less than about
7%, 6,5%, 6% or 5,5% of mono-alkyl ester(s) of saturated fatty
acids, based on the total weight of mono-alkyl-esters of fatty
acids in the composition.
[0027] The present invention also relates to a new
rapeseed alkyl-ester(s) composition further comprising (having
regard to anyone of the compositions of the invention) less
than about 15%, 14%, 13%, 12%, 11%, 10%, 9% or 8%, preferably
less than about 7% or 6% of mono-alkyl ester(s) of linoleic
acid, and/or less than about 20%, 19%, 18%, 17% or 16%,
preferably less than about 7,5% of mono-alkyl ester(s) of poly-
unsaturated fatty acids, based on the total weight of mono-
alkyl-esters of fatty acids in the composition.
[0028] The present invention also relates to a new
rapeseed alkyl-ester(s) composition comprising between about 7%
and about 6%, preferably between about 7% and about 5%, more
preferably between about 6,5% and about 5,5% of mono-alkyl
ester of saturated fatty acids. Said rapeseed alkyl-ester(s)
composition may further comprise between about 72% and about
85% of mono-alkyl ester of oleic acid, and/or between about 4%
and about 1% of mono-alkyl ester of linolenic acid, and/or
between about 15% and about 6% of mono-alkyl ester of linoleic
acid, and/or' between about 20% and about 7,50 of mono-alkyl
ester of poly-unsaturated fatty acids.
[0029] As used in the context of the present invention,
the term "about" means +/- 0,3%, unless the context clearly
dictates otherwise. For example, "about 7%" includes 6,7%,
6,8%, 6,9%, 7,1%, 7,2%, 7,3% and any real number comprised
between 6,7% and 7,3%.
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[0030] In a preferred composition of the invention, the
mono-alkyl esters of said saturated fatty acids comprise less
than 4,5%, preferably less than about 4%, and more preferably
less than about 3,5% of alkyl-ester(s) of palmitic acid, based
on the total weight of mono-alkyl-esters of fatty acids in the
composition.
[0031] In a preferred composition of the invention, the
mono-alkyl esters of said saturated fatty acids comprise
between about 4,5% and about 3%, preferably between about 4,1%
and about 3,5% of alkyl-ester(s) of palmitic acid, based on the
total weight of mono-alkyl-esters of fatty acids in the
composition.
[0032] In a preferred composition of the invention, the
mono-alkyl esters of fatty acids are methyl ester, ethyl ester,
propyl ester, or butyl ester of fatty acids. They may also
consist of a mixture of two, three or four of said esters.
[0033] In a more preferred composition, the mono-alkyl
esters of fatty acids are ethyl ester and / or methyl ester of
fatty acids, and more preferably methyl ester of fatty acids.
[0034] In a preferred composition, the mono-alkyl esters
of saturated fatty acids are methyl esters, ethyl esters,
propyl esters or butyl esters of saturated fatty acids. They
may also consist of a mixture of two, three or four of said
esters.
[0035] In a preferred composition, the mono-alkyl esters
of oleic acid are methyl ester, ethyl ester, propyl ester or
butyl ester of oleic acid. They may also consist of a mixture
of two, three or four. of said esters.
[0036] In a preferred composition, the mono-alkyl esters
of linolenic acid are methyl ester, ethyl ester, propyl ester,
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or butyl ester of linolenic acid. They may also consist of a
mixture of two, three or four of said esters.
[0037] In a more preferred composition, the mono-alkyl
esters of saturated fatty acids, of oleic acid or of linolenic
acid are respectively methyl esters, and/or ethyl esters of
said fatty acids.
[0038] And even more preferably, the mono-alkyl esters
are methyl esters of saturated fatty acids, of oleic acid or of
linolenic acid.
[0039] A preferred composition of the invention
comprises less than about 7% of ethyl esters of saturated fatty
acids based on the total weight of alkyl esters of fatty acids
in the composition.
[0040] A preferred composition of the invention
comprises more than about 73% of ethyl ester of oleic acid and
less than about 7% of ethyl esters of saturated fatty acids
based on the total weight of alkyl esters of fatty acids in the
composition.
[0041] A preferred composition of the invention
comprises less than about 3% of ethyl ester of linolenic acid
and less than about 7% of ethyl esters of saturated fatty acids
based on the total weight of alkyl esters of fatty acids in the
composition.
[0042] A more preferred composition of the invention
comprises less than about 7% of methyl esters of saturated
fatty acids, based on the total weight of alkyl esters of fatty
acids in the composition.
[0043] A more preferred composition of the invention
comprises more than about 73% of methyl ester of oleic acid
and/or less than about 3% of methyl ester of linolenic acid,
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and less than about 7% of methyl esters of saturated fatty
acids, based on the total weight of alkyl esters of fatty acids
in the composition.
[0044] A more preferred composition of the invention
5 comprises more than about 80% of methyl ester of oleic acid
and/or less than about 3% of methyl ester of linolenic acid,
and less than about 7% of methyl esters of saturated fatty
acids, based on the total weight of alkyl esters of fatty acids
in the composition.
10 [0045] A preferred composition of the invention
comprises less than about 2%, or less than about 1,5%,
preferably less than about 1% of methyl ester of linolenic acid
and less than about 7% of ethyl esters of saturated fatty
acids, based on the total weight of alkyl esters of fatty acids
in the composition.
[0046] A preferred composition of the invention
comprises:
- between about 75% and about 85%, preferably more than about
80% of methyl ester of oleic acid, and/or
- between about 2% and about 1%, preferably less than about
1,5% of methyl ester of linolenic acid, and
- less than about 7%, preferably between about 7% and about
5%, more preferably between about 7% and about 5,5% of ethyl
esters of saturated fatty acids,
based on the total weight of alkyl esters of fatty acids in the
composition.
[0047] The present invention also relates to a new
rapeseed alkyl-ester(s) composition comprising more than about
72%; 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%,
84%, 85%, 86%, 87%, 88%, 89%, or 90% of mono-alkyl ester(s) of
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oleic acid and/or less than about 4%, 3,5%, 3%, 2,5%, 2%, 1,5%
or 1% of mono-alkyl ester(s) of linolenic acid, and less than
about 7% of ethyl esters of saturated fatty acids, and less
than about 15%, 14%, 13%, 12%, 11%, 10%, 9% or 8%, preferably
less than about 7% or 6% of mono-alkyl ester(s) of linoleic
acid based on the total weight of mono-alkyl-esters of fatty
acids in the composition.
[0048] A preferred rapeseed alkyl-ester(s) composition
of the invention may comprise more than about 75% of mono-alkyl
ester(s) of oleic acid, less than about 2,5% of mono-alkyl
ester(s) of linolenic acid, less than about 7% of mono-alkyl
ester(s) of saturated fatty acids. It may further comprise less
than about 13% of mono-alkyl ester(s) of linoleic acid, and/or
less than about 16% of mono-alkyl ester(s) of poly-unsaturated
fatty acids, based on the total weight. of mono-alkyl-esters of
fatty acids in the composition.
[0049] A preferred rapeseed alkyl-ester(s) composition
of the invention comprises more than about 85% of mono-alkyl
ester(s) of oleic acid, less than about 2% of mono-alkyl
ester(s) of linolenic acid, less than about 6,5% of mono-alkyl
ester(s) of saturated fatty acids, based on the total weight of
mono-alkyl-esters of fatty acids in the composition.
[0050] A process for preparing a composition according
to the invention comprises a transesterification step of an
rapeseed oil comprising less than about 7%, preferably less
than about 6,50 of saturated fatty acids, based upon the total
weight of fatty acids present in the oil.
[0051] A process for preparing a composition according
to the invention comprises a transesterification step of an
rapeseed oil comprising at least about 72%; 73%, 74%, 75%, 76%,
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77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, or 85% of oleic acid
and/or less than about 4%, 3,5%, 3%, or 2% of linolenic acid,
and less than about 7%, preferably less than about 6,5%, and
more preferably less than about 6% of saturated fatty acids,
based upon the total weight of fatty acids present in the oil.
[0052] A process for preparing a composition according
to the invention comprises a transesterification step of an
rapeseed oil comprising:
- at least about 72%; 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%,
81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, or 90% of oleic
acid, and / or
- less than about 4%, 3,5%, 3%, 2,5%, 2%, 1,5% or 1% of
linolenic acid,
- and less than about 7%, preferably less than about 6,5%, 6%
or 5,5% of saturated fatty_acids, and optionally
- less than 15%, 14%, 13%, 12%, 11%, 10%, 9% or 8%,
preferably less than about 7% or 6% of linoleic acid, and
optionally
- less than 20%, 19%, 18%, 17% or 16%, preferably less than
about 7,5% of poly-unsaturated fatty acids,
based on the total weight of fatty acids in the oil.
[0053] The transesterification may consist of a base
catalysed transesterification of the rapeseed oil. This
reaction is more commonly used today, since it requires low
temperature and pressure conditions, and it yields very high
conversion with minimal side reactions and minimal reaction
time. Moreover, it is a direct conversion to mono-alkyl ester
with no intermediate compounds.
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[0054] The catalyst is generally sodium hydroxide or
potassium hydroxide. It is generally dissolved in the
alcohol(s) using a standard agitator or mixer.
[0055] The alcohol(s) can be methanol, ethanol, propanol
and/or butanol. Excess alcohol is normally used to ensure total
conversion of the rapeseed oil to its esters.
[0056] The alcohol(s) / catalyst mix is then charged
into a closed reaction vessel and the rapeseed oil is added.
[0057] The system should be closed to the atmosphere to
prevent the loss of the alcohol(s).
[0058] The reaction time may vary from 1 to 8 hours,
depending on the temperature. The temperature is preferably
chosen in the range consisting of the room temperature up to
the temperature just above the boiling point of the alcohol
used.
[0059] The conversion can be repeated (twice, three
times or more) in order to raise the yield and obtain the
required degree of purity, and to get very low glycerides
content.
[0060] Once the reaction is complete, two phases
containing respectively glycerin and alkyl esters can be
separated. The glycerin phase being much more dense than the
other, the two phases can be separated using merely the
gravity, or faster by using a centrifuge.
[0061] Each of the phases has substantial amount of the
excess alcohol(s) that was used in the reaction. This excess
alcohol(s) can be removed by any appropriate process, for
example with a flash evaporation process or by distillation.
[0062] The products of the reaction can be neutralized
before or after the two phases, containing respectively
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glycerin and esters, are separated. This neutralization step
can also take place before or after the alcohol(s) is (are)
removed in each phase.
[0063] The alkyl esters composition thus obtained can be
washed gently with warm water to remove residual catalyst or
soaps.
[0064] It can also be distilled in an additional step to
remove small amounts of colour bodies to produce a colourless
composition.
[0065] The glycerin by-product can be submitted to
further steps depending on the applications envisaged and the
degree of purity required.
[0066] In a preferred embodiment, the alcohol used is
methanol or ethanol. A mixture of both can be used and the
ester composition obtained is thus a mixture of methyl ester
and ethyl ester of fatty acids.
[0067] In a more preferred embodiment, methanol is used.
And when methanol is used the transesterification step can be
referred to as a methanolyse step.
[0068] The transesterification may also consist of a
direct acid catalysed transesterification of the rapeseed oil.
[0069] The alcohol can be methanol, ethanol, propanol
and/or butanol.
[0070] In a preferred embodiment, the alcohol used is
methanol, ethanol or a mixture of both.
[0071] Where methanol is used, the transesterification
step can also be referred to as a methanolyse step.
[0072] The transesterification may also consist of a two
steps reaction, the first being the conversion of the rapeseed
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oil to its fatty acids, and then the conversion of the fatty
acids to alkyl esters with acid catalysis.
[0073] The alcohol can be methanol, ethanol, propanol
and/or butanol.
5 [0074] In a preferred embodiment, the alcohol used is
methanol, ethanol or a mixture of both. The transesterification
step can also be referred to as a methanolyse step where
methanol is used.
[0075] Whatever are the catalysts used and/or the
10 alcohols used, the rapeseed oil used in a process of the
invention, comes from an oil (extracted from rapeseed
varieties) that comprises less than about 7%, preferably less
than about 6,5%, 6% or 5,5% of saturated fatty acids. Said oil
may further comprise either:
15 - at least about 72%; 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%,
81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, or 90% of oleic
acid, or
- less than about 4%, 3,5%, 3%, 2,5%, 2%, 1,5% or 1% of
linolenic acid, or
- less than about 15%, 14%, 13%, 12%, 11%, 10%, 9% or 8%,
preferably less than about 7% or 6% of linoleic acid, or
- less than about 20%, 19%, 18%, 17% or 16%, preferably less
than about 7,5% of poly-unsaturated fatty acids,
based upon the total weight of fatty acids present in the oil.
[0076] Said rapeseed oil can have a saturated fatty
acids content comprised between about 7% and about 6%,
preferably between about 7% and about 5%, more preferably
between about 7% and about 5,5% and can further comprise
between about 72% and about 85% of oleic acid, and/or between
about 4% and about 1% of linolenic acid, and/or between about
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15% and about=6% of linoleic acid, and/or between about 20% and
about 7,5% of poly-unsaturated fatty acids, based upon the
total weight of fatty acids present in the oil.
[0077] A variety from which such oil can be extracted
may be Brassica napus varieties. In particular it can be
extracted from varieties chosen from the group consisting of
CONTACT, CABRIOLET, CALIDA, MSP05, MSP11 and MSP13 varieties,
which are registered varieties, MSP11 and MSP13 excepted.
[0078] MSP11 variety is maintained as a Budapest Treaty
patent deposit with NCIMB under accession number NCIMB 41234
made July 9, 2004 by Monsanto S.A.S, Centre de Recherche de
Boissay, 28310 Toury, France.
[0079] MSP13 variety is maintained as a Budapest Treaty
patent deposit with NCIMB under accession number NCIMB 41237
made July 23, 2004 by Monsanto S.A.S, Centre de Recherche de
Boissay, 28310 Toury, France.
[0080] MSP05 and CALIDA varieties are also maintained as
a Budapest Treaty patent deposit with NCIMB respectively under
accession number NCIMB 41233 and 41235 made July 9, 2004 by
Monsanto S.A.S, Centre de Recherche de Boissay, 28310 Toury,
France.
[0081] A mixture of the oil extracted from two, three,
four, five or six of these varieties can also be used to
prepare a composition of the invention.
[0082] A preferred rapeseed oil comprises more than
about 73% of oleic acid and/or less than about 3,5% of
linolenic acid, and less than about 7% of saturated fatty
acids, based upon the total weight of fatty acids present in
the oil.
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[0083] A more preferred rapeseed oil comprises more than
about 75% of oleic acid and/or less than about 3% of linolenic
acid, and less than about 7% of saturated fatty acids, based
upon the total weight of fatty acids present in the oil.
[0084] A more preferred rapeseed oil comprises more than
about 75% of oleic acid and less than about 2,5% of linolenic
acid, and less than about 7% of saturated fatty acids, based
upon the total weight of fatty acids present in the oil.
[0085] A more preferred rapeseed oil comprises between
about 75% and about 85% of oleic acid and/or between about 2,5%
and about 1% of linolenic acid, and between about 7% and about
5%, preferably between about 7% and about 5,5% of. saturated
fatty acids, based upon the total weight of fatty acids present
in the oil.
[0086] A variety from which such oil can be extracted
may be chosen from the group consisting of MSP05, MSP11 and
MSP13 varieties.
[0087] A more preferred rapeseed oil comprises more than
about 80% of oleic acid and less than about 20 of linolenic
acid, and less than about 7%, preferably less than about 6% of
saturated fatty acids, based upon the total weight of fatty
acids present in the oil.
[0088] A more preferred rapeseed oil comprises more than
about 85% of oleic acid and/or less than about 2% of linolenic
acid, and less than 6,5% of saturated fatty acids, based upon
the total weight of fatty acids present in the oil.
[0089] A variety from which such oil can be extracted is
for example MSPll variety or MSP13 variety.
[0090] In a preferred rapeseed oil, the said saturated
fatty acids comprise less than 4,5%, preferably less than about
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4%, more preferably less than about 3,5% of palmitic acid based
upon the total weight of fatty acids present in the oil.
[0091] In a preferred rapeseed oil, the said saturated
fatty acids comprise between about 4,5% and about 3%, more
preferably between about 4,1% and about 3,5% of palmitic acid
based upon the total weight of fatty acids present in the oil.
[0092] A process of the invention may comprise, prior to
the transesterification step, the steps of degumming the crude
rapeseed oil, and of refining the resulting oil.
[0093] Crude oil is degummed to remove bulk of certain
phosphatides such as lecithin.
[0094] The degumming treatment can consist of mixing the
rapeseed oil with water or steam during a certain period of
time, preferably about 30 min. to about 60 min., at a
temperature between about 500 and about 90 C, preferably in
presence of phosphoric acid, citric acid or other acidic
materials. The gummy residue is dehydrated and the precipitated
gums are removed by decantation or centrifugation.
[0095] The degumming step may also consist of a chemical
process.
[0096] The oil thus obtained is refined (or neutralized)
in order to reduce the free fatty acids, phospholipids,
carbohydrates or proteins.
[0097] The most widely practiced form of refining method
is an alkali treatment, usually sodium hydroxide, by which the
free fatty acids are converted into water soluble soaps.
Phospholipids, carbohydrates and proteins can also be changed
to water soluble substances with hydration.
[0098] After the alkali treatment, the rapeseed oil is
washed with (hot) water to remove residual water soluble soaps
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that can reduce stability of the oil. In addition, pigments of
the oil, such as chlorophyll, also undergo partial
decomposition during this step.
[0099] The refining step can also be referred to as a
neutralization step.
[00100] A process of the invention may also comprise a
bleaching step, after the refining step and before the
transesterification step. In fact, a large amount of the
colouring materials, such as chlorophyll and carotene, is
already removed during the refining process. And the bleaching
step aims to finalize the decolouration process.
[00101] A common method of bleaching is by absorption of
the colour producing substances on an adsorbent material such
as e.g. bentonite (or acid-activated earth clay), Fuller's
earth, TONSIL earth, silica gel, etc.
[00102] A process of the invention may also comprise a
step of extracting the oil from the rapeseed.
[00103] Oil extraction methods are well known and can be
mechanical, via solvents (generally hexane), via enzymes and/or
by means of high pressure CO2.
[00104] A composition obtained by a process of the
invention comprises less than about 7%, 6,5% or 6% of mono-
alkyl-esters of saturated fatty acids, in particular methyl
ester of saturated fatty acid, based on the total weight of
mono-alkyl esters of fatty acids in the composition.
[00105] A composition obtained by a process of the
invention comprises more than about 72%; 73%, 74%, 75%, 76%,
77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%
or 90% of mono-alkyl ester(s) of oleic acid, in particular
methyl ester of oleic acid, and/or less than about 4%, 3,5%,
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3%, 2,5%, 2%, 1,5% or 1% of mono-alkyl ester(s) of linolenic
acid, in particular methyl ester of linolenic acid, and less
than about 7%, 6,5%, 6% or 5,5% of mono-alkyl-esters of
saturated fatty acids, in particular methyl ester of saturated
5 fatty acid, based on the total weight of mono-alkyl esters of
fatty acids in the composition. All the combinations are
envisaged for a composition of the invention.
[00106] A composition obtained by a process of the
invention may also contain small amount or traces of alkyl
10 ester of palmitoleic acid, alkyl ester of stearic acid, alkyl
ester of arachidic acid, alkyl ester of eicosenoic acid, alkyl
ester of behenoic acid, alkyl ester of erucic acid, and/or
mono-, di-. and/or tri-glyderides.
[00107] A possible use of a composition according to the
15 present invention is as biodiesel.
[00108] A composition of the invention suitable for this
use preferably comprises less than about 7%, preferably less
than about 6,5%, 6% or 5,5% of ethyl esters of saturated fatty
acids, based on the total weight of alkyl esters of fatty acids
20 in the composition.
[00109] A composition of the invention suitable for this
use preferably comprises more than about 75% of ethyl ester of
oleic acid and less than about 7%, preferably less than about
6,5%, 6% or 5,5% of ethyl esters of saturated fatty acids,
based on the total weight of alkyl esters of fatty acids in the
composition.
[00110] A composition of the invention suitable for this
use preferably comprises less than about 3% of ethyl ester of
linolenic acid and less than about 7%, preferably less than
about 6,5%, 6% or 5,5% of ethyl esters of saturated fatty
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21
acids, based on the total weight of alkyl esters of fatty acids
in the composition.
[00111] A composition of the invention suitable for this
use preferably comprises more than about 72%; 73%, 74%, 75%,
76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%,
88%, 89% or 90% of ethyl ester of oleic acid, less than about
4%, 3, 5 0, 3%, 2,5%, 2%, 1, 5 0 or 1% of ethyl ester of linolenic
acid, and less than about 7%, preferably less than about 6,5%,
6% or 5, 5 0 of ethyl esters of saturated- fatty acids, based on
the total weight of alkyl esters of fatty acids in the
composition.
[00112] A composition of the invention suitable for this
use preferably comprises more than about 75%, preferably
between about 75% and about 85% of ethyl ester of oleic acid
and/or less than about 3%, preferably between about 3% and
about 1% of ethyl ester of linolenic acid, and less than about
7%, 6,5% or 6%, preferably between about 7% and about 5%, more
preferably between about 7% and about 5,5% of ethyl esters of
saturated fatty acids, based on the total weight of alkyl
esters of fatty acids in the composition.
[00113] A composition of the invention suitable for this
use preferably comprises more than about 75% of ethyl ester of
oleic acid and less than about 3% of ethyl ester of linolenic
acid, and less than about 7% of ethyl esters of saturated fatty
acids, based on the total weight of alkyl esters of fatty acids
in the composition.
[00114] A composition of the invention suitable for this
use preferably comprises less than about 7%, preferably less
than about 6,5%, 6% or 5,5% of methyl esters of saturated fatty
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22
acids, based on the total weight of alkyl esters of fatty acids
in the composition.
[00115] A composition of the invention suitable for this
use more preferably comprises more than about 72%; 73%, 74%,
75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%,
87%, 88%, 89% or 90% of methyl ester of oleic acid, less than
4%, 3,5%, 3%, 2,5%, 2%, 1,5% or 1% of methyl ester of linolenic
acid, and less than about 7%, 6,5%, 6% or 5,5% of methyl esters
of saturated fatty acids based on the total weight of alkyl
esters of fatty acids in the composition.
[00116] A composition of the invention suitable for this
use more preferably comprises more than about 72%; 73%, 74%,
75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%,
87%, 88%, 89% or 90% of methyl ester of oleic acid and less
than about 7%, 6,5%, 6% or 5,5% of methyl esters of saturated
fatty acids based on the total weight of alkyl esters of fatty
acids in the composition.
[00117] A composition of the invention suitable for this
use more preferably comprises less than about 4%, 3,5%, 3%,
2,5%, 2%, 1,5% or 1% of methyl ester of linolenic acid and less
than about 7%, 6,5%, 6% or 5,5% of methyl esters of saturated
fatty acids based on the total weight of alkyl esters of fatty
acids in the composition.
[00118] A composition of the invention suitable for this
use more preferably comprises more than about 75% of methyl
ester of oleic acid and less than about 7% of methyl-ester of
saturated fatty acids, based on the total weight of alkyl
esters of fatty acids in the composition.
[00119] A composition of the invention suitable for this
use more preferably comprises less than about 3% of methyl
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ester of linolenic acid and less than about 7%, 6,5%, 6% or
5,5% of methyl-ester of saturated fatty acids, based on the
total weight of alkyl esters of fatty acids in the composition.
[00120] A composition of the invention suitable for this
use more preferably comprises more than about 75%, preferably
between about 75% and about 85% of methyl ester of oleic acid,
and/or less than about 3%, preferably between about 3% and
about 1% of methyl ester of linolenic acid, and less than about
7%, preferably between about 7% and about 5%, more preferably
between about 7% and about 5,5% of methyl-ester of saturated
fatty acids, based on the total weight of alkyl esters of fatty
acids in the composition.
[00121] A composition of the invention suitable for this
use may also comprise more than about 73% of methyl- and/or
ethyl-ester of oleic acid and/or less than about 3% of methyl-
and/or ethyl-ester of linolenic acid, and less than about 70,
6,5%, 6% or 5,5% of methyl- and/or ethyl-ester of saturated
fatty acids, based on the total weight of alkyl esters of fatty
acids in the composition.
[00122] A composition of the invention suitable for this
use may also comprise less than 15%, 14%, 13%, 12%, 11%, 10%,
9% or 8%, preferably less than about 7% or 6% of methyl- and/or
ethyl ester(s) of linoleic acid, based on the total weight of
mono-alkyl-esters of fatty acids in the composition.
[00123] A composition of the invention suitable for this
use may also comprise less than about 20%, 19%, 18%, 17% or
16%, preferably less than about 7,5% of mono-alkyl ester(s) of
poly-unsaturated fatty acids, based on the total weight of
mono-alkyl-esters of fatty acids in the composition.
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[00124] Prior to use as a commercial biodiesel, the
composition of the invention must be analysed to ensure it
meets the specifications established by the European Union, the
American Society for Testing and Materials (ASTM) or other
national or international instances.
[00125] The most important parameters (or specifications)
can be summed up in the following table (Table I), together
with the methods used in the examples section to measure said
parameters.
Table I
Parameters Methods Units
Ester content HPLC o mass
Cetane Number L.C. NF EN ISO -
5165 ASTM D 613
Kinematic Viscosity (40 C) ISO 3104 mm2/s
Pourpoint ISO 3016 C
Water content Karl-fisher mg/kg
Acid Number NF T 60-204 mg KOH/g
Saponification Number NF ISO 3657 mg KOH/g
Iodine Value NF ISO 3961 g 12/100 g
Peroxide Value NF T 60 220 meq 02/kg
Unsaponifiable matter NF T 60-205-1 %
Glycerides content HPLC %
Linolenic acid methyl ester Gas Chromatography %
Free glycerol HPLC %
Oxidation stability (110 C,
EN 14112 hours
10 1/h - TIR
[00126] A composition of the invention comprising less
than 7%, 6,5%, 6% or 5,5% of methyl esters of saturated fatty
acids and further comprising more than 72% of methyl ester of
oleic acid and/or less than 3% of methyl ester of linolenic
acid, based on the total weight of alkyl esters of fatty acids
in the composition, shows very good properties suitable for its
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use as biodiesel or as an additive in fuels. These properties
are summed up in the following table (Table II).
Table II ~
Rapeseed methyl Units
E.U. (prEN USA (ASTM
Parameters ester composition
of the invention 14214) D6751-02)
Ester content 98,6 to 99,5 >_96,5 - o mass
52,1 to 55,3
Cetane Number Or 52,1 to 57,2 ?51 _47 -
Kinematic Viscosity (40 C) 4,58 to 4,87 3,5 to 5 1,,9 to 6,0 mm2/s
Pourpoint -12,5 to -16 <0 C
Water content <500 <_500 mg/kg ~
Acid Number 0,04 to 0,10 <0,5 <_0,8 mg KOH/g N
187,9 to 191,8 Ln
Saponification Number Or 185,7 to 191,8 - - mg KOH/g N
Iodine Value 88,9 to 105,4 <120 - g 12/100 g 0
0
rn
4,1 to 8,7 IH
Peroxide Value - - meq 02/kg N
Or 2,13 to 8,7
0,78 to 0,83
Unsaponifiable matter Or 0,65 to 0,83
Linolenic acid methyl ester 0,84 to 9,60 <_12 0
1,3 to 1,4 ti
Glycerides content <1,2 - %
Or 1,0 to 1,4
Free glycerol traces <0,02 <_0,02
Phosphorus content <10 _10 <10 mg/kg
Oxidation stability 5 to 18,5 >_6 - hours
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[00127] Having regard to a rapeseed methyl ester
composition of the invention, few parameters can be noticed as
remarkable, in particular the cetane number, the oxidation
stability, the iodine value and the pour point of said
composition.
[00128] The cetane number is a relative measure of the
interval between the beginning of injection and auto-ignition
of the fuel. The higher the number, the shorter the delay
interval. Fuels with low cetane numbers will cause hard
starting, rough operation, noise and exhaust smoke.
[00129] In view of its cetane number, a composition of
the invention will help diesel engines to operate better.
[00130] The iodine value of an oil is normally associated
with the potential for the oil to polymerise, as it is a
measure of the proportion of unsaturated bonds. It is admitted
that the use of biodiesel with an iodine number that exceeds
115 increases the risk that the engine lubricating oil will
polymerise over time.
[00131] In view of the iodine value of a composition
according to the present invention, the risk of polymerization
will be drastically diminished when using said composition.
[00132] The good oxidation stability showed by the
compositions of the invention means that the risks of
generating hydroperoxide is diminished, preventing the
peroxidation chain mechanism which damages the fuel system
components. It is also an indication that the fuel darkening
and the formation of insolubles, sediment and gum will be
substantially attenuated.
[00133] The pour point of a composition of the invention
indicates a good biodiesel cold weather performance.
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[00134] A rapeseed alkyl ester composition of the
invention may also be used as a solvent, for example to
dissolve petroleum.
[00135] The invention will be illustrated with further
details in the following examples, which should not be
construed as limiting the scope of the invention in any way.
EXAMPLES
Example 1: Oil extraction
a). Mechanical extraction
[00136] The rapeseed oil are pressed in a single screw
press, Taby 40A press, with a diameter of 6,5 mm, at a
temperature comprised between about 40 and about 60 C.
[00137] The following varieties are pressed: CONTACT,
CABRIOLET, CALIDA, MSP05 and MSP11 varieties.
[00138] The result of that step can be summarized in the
following table (Table III).
Table III.
Varieties CARACAS CONTACT CABRIOLET CALIDA MSP05 MSP11
Seeds, kg 19,4 19,2 19,5 14,9 19,3 19,5
Dry matter,
kg 18,34 17,84 18,32 14,06 18,21 18,33
Theoretical
oil, kg 8,93 8,35 8,73 6,40 8,57 8,28
Non filtered 6,8 6,7 6,5 3,8 6,4 6,6
oil, kg
Yield, 76,14 80,23 74,46 59,38 74,68 72,3
Oil cake, kg 11,9 12,3 12,8 10,3 12,7 13,0
Easy to press
/ Difficult Easy Easy Easy eNot
asy Easy Easy
to press
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[00139] In this example and in the following examples,
the CARACAS variety is used as a point of reference.
[00140] It can be noted that the yields are very high,
between about 70% and about 75%, except for CALIDA variety.
b). Hexane extraction
Material of extraction
[00141] Extractor 5L, a thermic bath and an extraction
cartridge 13L
Conditions of the extraction
[00142] The temperature of the bath is set at 82,5 C for
a flow rate of hexane of about 2 L/h. The extraction process
lasts about 16 hours. Because of the important amount of oil
cake, the extraction process is repeated twice. The hexane
contained in the cartridge is used again for second extraction,
which lasts 17 hours.
[00143] The oil extracted mechanically, and the oil
extracted with hexane are mixed and filtered on a settling in
order to remove the solid particles. The oil is then distilled
on a"R10" at a temperature of 90 C, 100 mbar during 1 hour.
The flow rate of hexane is about 2 1/h. The residual content of
hexane is about 4% to about 6%, which will facilitate the
further steps of purification process.
[00144] The results of the extraction steps are
summarized in the following table (Table IV)
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Table IV.
Varieties CARACAS CONTACT CABRIOLET CALIDA MSP05 MSP11
Crude oil, kg 9,3 8,5 8,8 6,2 8,7 8,0
Hexane
content, 0 6,03 1,9 1,3 3,2 4,4 2,2
Yield, %(*) 97,4 99,53 99,68 93,37 97,0 97,3
(*) based on the total oil content in the seeds.
5 Example 2: Degumming step.
[00145] The degumming and the neutralization are both
carried out in 10 litres temperature controlled reaction
vessel.
10 [00146] In order to facilitate the degumming, mainly the
decantation, the residual hexane content is adjusted at 6%.
[00147] The degumming step aims to remove the
phospholipids naturally present in the crude oil.
[00148] The oil is introduced in the reaction vessel,
15 then the temperature is raised up to 65 C while the oil is
agitated. At 65 C, phosphoric acid (1,500) and water (6% based
on the oil weight) are added. The mixture is agitated during 10
min. and then the temperature is raised up to 75 C. The mixture
is agitated at this temperature of 75 C during 30 min. Then,
20 the decantation is allowed to proceed during 30 min. Finally,
the heavier phase is removed.
[00149] The results of this step are summarized in the
following table (Table V).
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Table V.
Variety CARACAS CONTACT CABRIOLET CALIDA MSP05 MSP11
Dry crude oil, g 8,7 8,3 8,5 5,7 8,2 7,73
H3PO4 at 75%, g 17,4 16,7 17,1 11,4 16,5 15,5
H20, g 521 500 512 343 494 464
Decantation Very correct good correct correct correct
good
Example 3: Refining or neutralization step.
[00150] This step aims to remove the free fatty acids
present in the degummed oil.
[00151] The degummed oil is maintained at 75 C in a
reaction vessel in which sodium hydroxide is added in excess of
10% compared to theoretical amount needed and the mixture is
agitated during 5 min.
[00152] Then the temperature is raised up to 95 C and
maintained at 95 C during 30 min. The reaction vessel is cooled
down at 65 C and the two phases of the reaction mixture are
allowed to separate by gravity during 20 min.
[00153] Then the aqueous phase is withdrawn (pH of 11-12)
and the oil is washed with demineralized water until the used
water is neutral.
[00154] The oil is then dried at 110 C under vacuum
during 30 min.
[00155] The process and the results are summarized in the
following table (Table VI)
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Table VI.
Variety: CARACAS CONTACT CABRIOLET CALIDA MSP05 MSP11
NaOH 98,63 %, g 4,00 8,28 2,78 3,52 2,73 3,25
H2O, g 521 500 512 343 494 464
Washing steps 3 5 4 4 3 4
Phases Good separation, aqueous phase very dark, interface
separation with flocs.
Degummed Oil, kg 8.7 8.3 8.5 5.7 8.2 7,73
Acid number of
the degummed 0,26 0,96 0,37 0,55 0,33 0,32
oil, mg KOH/g
Refined Oil, kg 8.3 7.3 7.9 5.1 7.5 7,58
Acid number of
the refined oil, 0,17 0,27 0,14 0,17 0,12 0,13
mg KOH/g
Yields, 0 95,40 87,95 92,94 89,47 91,46 98,06
[00156] The varieties have all a low acid number: below 1
mg KOH/g. Usually, the acid number of common rapeseed oil is
about 2 to about 3,5 mg KOH/g.
[00157] With an acid number below 0,3 mg KOH/g, the
degumming and refining steps are regarded as very efficient.
Example 4: Bleaching step.
[00158] The refined oil is introduced in the reaction
vessel with 3%, based on the weight of the oil, of TONSIL
earth.
[00159] The temperature is raised up to 95 C under vacuum
with a pressure of 200 mbar. After 15 min. the pressure is
diminished to 100 mbar and then to 15 mbar after 10 min.
[00160] The decolouration continues at 95 C, 15 mbar
during 2 hours, and then the temperature is reduced to a
temperature of 60 C. At 60 C, 0,5% of promosil, based on the
weight of the oil, is added to improve the filtration, which is
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33
carried out on a filter ("cloche" filter), at a flow rate of
about 20L/h.
[00161] The oil is then cooled down with the ambient
temperature during 1 hour and stored under nitrogen atmosphere.
[00162] The results of the bleaching step are summarized
in the following table (Table VII).
Table VII
Variety CARACAS CONTACT CABRIOLET CALIDA MSP05 MSP11
Refined oil, g 5160 4230 4806 4990 4880 3684
Acid number of
the refined oil 0,17 0,27 0,14 0,17 0,12 0,13
(mg de KOH/g)
Bleached Oil, g 4930 4100 4514 4800 4650 3508
Acid number of
the bleached oil 0,22 0,32 =0,22 0,2 0,20 0,20
(mg de KOH/g)
Yield, % 95,54 96,93 93,92 96,19 95,29 95,22
[00163] The bleaching step using TONSIL earth has a small
impact on the acid numbers, which are slightly higher in
comparison with the acid numbers before this bleaching step.
Example 5: Fatty acids content.
[00164] The fatty acids content of the oils extracted
from the different rapeseed varieties have been evaluated by
gas chromatography and the results are summarized in the
following table (Table VIII).
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Table VIII
Fatty acids CARACAS CONTACT CABRIOLET CALIDA MSP05 MSP11
C16:0 Palmitic 4,99 3,89 3,81 3,57 4,33 3,38
C16:1 Palmitoleic - - 0,23 0,14 0,31 0,29
C18:0 Stearic 1,60 1,55 1,55 1,57 1,64 2,09
C18:1 Oleic 63,15 73,36 76,87 63,23 75,92 84,91
C18:2 Linoleic 17,73 9,29 7,98 28,65 12,76 5,47
C18:3 (n-6) gamma - - - - - -
Linolenic
C18:3 (n-3) alpha 10,62 9,81 7,88 0,80 2,75 2,01
Linolenic
C20:0 Arachidic 0,58 0,51 0,21 0,45 0,56 0,58
C20:1 Eicosenoic 1,03 1,14 1,01 1,08 1,14 1,08
C22:0 Behenic 0,30 0,36 0,46 0,34 0,39 -
C22:1 Erucic - 0,09 - 0,17 0,20 -
C24:0 Lignoceric - - - - -
C24:1 Nervonic - - - - -
Others - - - - - 0,19
Total 100 100 100 100 100 100
Saturated acid 7,47 6,31 6,03 5,93 6,92 6,05
Mono-unsaturated acid 64,18 74,59 78,11 64,62 77,57 86,28
Poly-unsaturated acid 28,35 19,1 15,86 29,45 15,51 7,48
Example 6: Methanolyse.
[00165] Approximately 2000 g of oil extracted from
rapeseed, degummed and refined according to the process
described in examples 2 and 3, is mixed with 300 g of methanol
in a reaction vessel. About 5 to 10 g of sodium hydroxide added
to the same reaction vessel.
[00166] The methanolyse takes place during about 2 hours,
at a temperature comprised between approximately 40 C and 60
C, under atmospheric pressure.
[00167] These conditions provide essentially about 95 %
conversion of added triglycerides to fatty acids methyl esters.
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[00168] After the settling, the two phases of the
reaction mixture are allowing to stand and separate to provide
methyl esters in the upper phase, and a mixture of glycerol and
approximately 2% wt. residual methyl esters, methanol, and base
5 in the lower phase. The upper phase is used in a second
conversion.
[00169] The same amount as in the first conversion of
methanol and of alkaline catalyst is then introduced in the
reaction vessel. The same conditions of temperature and
10 pressure are applied (between about 400 and 60 C, atmospheric
pressure) . In these conditions more than 98 % of triglycerides
are converted to fatty acids methyl esters.
[00170] The fatty acids methyl esters are washed and
dried. More than 1900 g of fatty acids methyl esters are,
15 weighted, with a purity of higher than 98%. The mass yield,
methyl esters / refined oil, is good.
[00171] The results of the methanolyse are summed up in,
the following table (Table IX).
Table IX
Variety CARACAS CONTACT CABRIOLET CALIDA MSP05 MSP11
18t % esters 98,3 98,6 94,0 93,9 98,1 68,53
% mono- (**) 0,7 0,8 3,77 2,0 0,6 1,47
conversion % di- (**) 1,0 0,5 2,27 2,5 0,9 8,72
yield % tri- (**) 0,1 0,1 0 2,4 0,4 21,29
2õd % esters 98,8 98.7 98,6 98,8 98,7 99,48
% mono- (**) 0 0,3 0,2 0,9 0,4 0,42
conversion o di- (**) 1,2 1,0 1,2 0,3 0,9 0,10
yield o tri- (**) 0 0 0 0 0 0
Refined 3029 2924 3173 1736 2514 3784
oil, g
Methyl 2972 2769 3010 1686 2407 3448
esters, g
Yield, % 98,12 95,70 94,98 97,12 95,74 91,12
(*)
20 (*)methyl esters / refined oil
(**) mono-, di-, tri-glycerides
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Example 7: Methyl esters content.
[00172] The methyl esters content of the rapeseed methyl
ester composition obtained by the process described in example
6 has been evaluated by gas chromatography and the results are
summarized in the following table (Table X).
Table X
Methyl ester CARACAS CONTACT CABRIOLET CALIDA MSP05 MSP11
C16:0 Palmitic 4,71 4,00 4,05 4,29 4,31 4,40
C16:1 Palmitoleic - 0,25 0,21 0,14 0,24 0,34
C18:0 Stearic 1,66 1,69 1,48 1,63 1,60 1,83
C18:1 Oleic 63,39 72,95 76,70 63,98 76,31 85,33
C18:2 Linoleic 17,66 9,15 8,12 27,29 12,74 5,32
C18:3 (n-6) gamma
Linolenic
C18:3 (n-3) alpha 10,47 9,60 7,60 0,84 2,64 1,97
Linolenic
C20:0 Arachidic 0,58 0,61 0,26 0,50 0,54 0,20
C20:1 Eicosenoic 0,91 1,05 1,02 1,05 1,06 0,61
C22:0 Behenic 0,62 0,63 0,56 0,28 0,56 -
C22:1 Erucic - 0,07 - - - -
C24:0 Lignoceric - - - - - -
C24:1 Nervonic - - - - - -
Others - - - - - -
Total 100,00 100,00 100,00 100,00 100,00 100,00
Saturated acids 7,57 6,93 6,35 6,70 7,01 6,43
Mono-unsaturated 64,30 74,32 77,93 65,17 77,61 86,28
acids
Poly-unsaturated 28,13 18,75 15,72 28,13 15,38 7,29
acids
Example 8: Specifications of a rapeseed methyl ester
composition for use as biodiesel.
[00173] The rapeseed methyl ester composition obtained
has been analysed and compared with the specifications of a
biodiesel as established by the European Union. The results of
such analysis are summed up in the following table (Table XI).
O
Table XI
Parameters Units E.U. CARACAS CONTACT CABRIOLET. CALIDA MSP05 MSP11
Ester content % mass 96,5 98,8 98,7 98,6 98,8 98,7 99,5
Cetane Number - a51 51,2 52,4 52,1 55,4 54,0 55,3
Kinematic Viscosity mm2/s 3,5 to 5 4,50 4,58 4,87 4,52 4,66 4,64
(40 C) Pourpoint C <0 -14,0 -16,0. -15 -16 -14,5 -12,5
Water content mg/kg <500 _<500 <_500 <_500 <_500 <500 5500.
Acid Number mg KOH/g <0,5 0,04 0,04 0,04 0,05 0,05 0,10
Saponification ~
Number mg KOH/g - 191,6 187,9 190,9 187,1 191,8 188,6
N
Iodine Value g 12/100 g <120 113,5 105,4. 101,8 104,8 96,0 88,9 Ln
Peroxide Value meq 02/kg - 6,2 6,7. 8,7 2,6 4,1 4,67
Unsaponifiable o
matter - 0,98 0,83 0,78 - 0,81 0,63 o
0
Linolenic acid o <12 10,47 9,60 7,60 0,84 2,64 2,0
methyl ester
Glycerides content % <_1,2 1,1 1,3 1,4 1,2 1,4 0,52 ~
Free glycerol o. <0,02 trace trace trace trace trace trace
Phosphorus content mg/kg <10 <10 S10 510 :510 <10 510
Oxidation stability hours z6 5,0 5,1 5,2 7,2 9,0 18,5
0
CA 02571724 2006-12-21
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38
[00174] Currently, methyl esters of rapeseed oil are used
with low methyl ester of oleic acid content. The cetane number
measured for such biodiesel can hardly reach 51.
[00175] As shown in Table XI, a rapeseed methyl ester
composition according to the invention has a very high quality,
with a cetane number higher than 51 and an iodine value pretty
below 120.
[00176] A preferred variety to be used to prepare a
rapeseed methyl ester composition of the invention is MSP05
[00177] A more preferred variety to be used to prepare a
rapeseed methyl ester composition of the invention is MSPil.
Example 9: a composition of the invention.
[00178] The oil is extracted from MSP13 varieties
according to a method as described in example 1.
[00179] The resulting oil is then degummed and refined
carrying out methods as described respectively in example 2 and
in example 3.
[00180] From 3,07 kg of seeds, 1,32 kg of crude oil is
obtained, and then 1,21 kg of refined oil.
[00181] Then a methanolyse as described in example 6 is
perfomed resulting in 1,16 kg of methyl esters.
[00182] The yields are regarded as excellent.
[00183] The methyl esters content of the rapeseed methyl
ester composition obtained from MSP13 by the process described
in example 6 has been evaluated by gas chromatography and the
results are summarized in the following table (Table XII).
CA 02571724 2006-12-21
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39
Table XII
Fatty acids Content wt.%
C16:0 Palmitic 3,40
C18:0 Stearic 1,59
C18:1 Oleic 83,44
C18:2 Linoleic 8,58
C18:3 Linolenic 1,36
C20:0 Arachidic 0,36
C20:1 Eicosenoic 1,10
C22:0 Behenic 0,17
Total 100,00
[00184] The rapeseed methyl ester composition obtained
has been analysed and compared with the specifications. of a
biodiesel as established by the European Union. The results of
such analysis are summed up in the following table (Table XIII)
Table XIII
Parameters Units E.U. MSP13
Ester content % mass a96,5 99
Cetane Number - a51 57,2
Kinematic Viscosity mm2/s 3,5 to 5 4,71
(40 OC)
Pourpoint C <0 -15,0
Water content mg/kg <500 <50
Acid Number mg KOH/g <0,5 0,07
Saponification
mg KOH/g - 185,7
Number
Iodine Value g 12/100 g <120 91,7
Peroxide Value meq 02/kg - 2,13
Unsaponifiable
matter - 0,65
Linolenic acid
methyl ester 512 1,36
Glycerides content o <1,2 1,0
Free glycerol % <0,02 0
Phosphorus content mg/kg <10 <5
Oxidation stability hours z6 16,2
