Note: Descriptions are shown in the official language in which they were submitted.
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USE OF A RAPESEED OIL IN BIOLUBRICANTS
Field of the invention
[0001] The present invention relates to the use of a
rapeseed oil as base fluid in (bio-)lubricant.
[0002] The present invention also relates to the use
of alkylesters derived from rapeseed oil as base fluid in
(bio-)lubricant.
Background
[0003] Lubricants can be defined as a preparation
(composition) made of base fluids and additives. The base
fluid, the major ingredient, contributes significantly to the
inherent properties of said lubricants such as the viscosity,
the lubricity, the pour point, the oxidative and thermal
stability, the hydrolytic stability, etc.
[0004] Mineral oil is the most commonly used base
fluid for all type of lubricants. Synthetic hydrocarbon such
as olefin oligomers are used in a wide range of applications
for their better oxidative stability.
[0005] The use of vegetable oils as base fluids for
obtaining bio-lubricants, exhibiting rapid biodegradability
and low environmental toxicity, is known but currently
limited because of their weak performance having regard in
particular to their oxidative stability, their hydrolytic
stability and their pour point.
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Sununary of the invention
[0006] The present invention provides a new
(bio-)lubricant comprising (or consisting of) rapeseed oil
and at least one additive, wherein the saturated fatty acids
content of said rapeseed oil is less than (about) 7%, 6,50,
6% or 5,5%, based upon the total weight of the fatty acids
present in the rapeseed oil.
[0007] Preferably, in a (bio-)lubricant according to
the invention, said rapeseed oil further comprises more than
(about) 72%, 75%, 80%, or 85% of oleic acid, and/or less than
(about) 4%, 3, 5 0, 3%, 2%, or 1% of linolenic acid, based upon
the total weight of the fatty acids present in the rapeseed
oil.
[0008] A(bio-)lubricant according to the invention
may further comprise another oleaginous oil, wherein the
ratio rapeseed oil to said other oleaginous oil is such that
the resulting oil comprises less than (about) 7%, 6,5%, 6% or
5,5% of saturated fatty acids, based upon the total weight of
the fatty acids present in said resulting oil.
[0009] Preferably, said ratio is such that said
resulting oil further comprises more than (about) 72%, 750,
80%, or 85% of oleic acid, and/or less than (about) 4%, 3, 5 0,
3%, 2%, 1% or 0,5% of linolenic acid, based upon the total
weight of the fatty acids present in said oil.
[0010] The ratio rapeseed oil to sunflower oil can be
comprised between 5/95 and 95/5.
[0011] In a (bio-)lubricant according to the
invention, said other oleaginous oil can be a sunflower oil,
preferably a High Oleic sunflower oil, and/or a soybean oil.
[0012] The present invention also provides a
(bio-)lubricant consisting of a base-fluid and at least one
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additive, said base-fluid consisting of a mono-alkyl esters
composition derived from (or resulting from the
transesterification of) rapeseed oil, comprising less than
(about) 7%, 6,5%, 6% or 5,5% of mono-alkyl esters of
saturated fatty acids, based upon the total weight of the
mono-alkyl esters of fatty acids present in said composition.
[0013] Preferably, said mono-alkyl esters composition
further comprises more than (about) 72%, 75%, 80%, or 85% of
mono-alkyl ester of oleic acid, and/or less than (about) 4%,
3, 5 0, 3 0, 2 o, or 1% of mono-alkyl ester of linolenic acid,
based upon the total weight of the mono-alkyl ester of fatty
acids present in said composition.
[0014] Another object of the invention is a
(bio-)lubricant consisting of a base-fluid and at least one
additive, said base-fluid consisting of a mono-alkyl esters
composition derived from (or resulting from the
transesterification of) rapeseed oil and another oleaginous
oil, comprising less than (about) 7%, 6,50, 6% or 5,5% of
mono-alkyl esters of saturated fatty acids, based upon the
total weight of the mono-alkyl esters of fatty acids present
in said composition.
[0015] Preferably, said base-fluid further comprises
more than (about) 72%, 75%, 80%, or 85% of mono-alkyl ester
of oleic acid, and/or less than (about) 4 0, 3, 5 0, 3%, 2%, 1 0
or 0,5% of mono-alkyl ester of linolenic acid, based upon the
total weight of the mono-alkyl ester of fatty acids present
in said base-fluid (or mono-alkyl esters composition).
[0016] Another object of the invention relates to the
use of a rapeseed oil comprising a saturated fatty acids
content of less than (about) 7%, 6,5%, 6 0 or 5,5% based upon
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the total weight of the fatty acids present in the rapeseed
oil, as a base fluid in (bio-)lubricants.
[0017] Preferably, for said use, said rapeseed oil
further comprises more than (about) 72%, 75%, 80 0, or 85% of
oleic acid, and/or less than (about) 4%, 3,50, 3%, 2%, or 1%
of linolenic acid, based upon the total weight of the fatty
acids present in the rapeseed oil.
[0018] Another object relates to the use of (a blend
of) a rapeseed oil and another oleaginous oil, wherein the
ratio rapeseed oil to said other oleaginous oil is such that
the resulting oil comprises less than (about) 7%, 6,5%, 6% or
5,5% of saturated fatty acids, based upon the total weight of
the fatty acids present in said resulting oil, as a base
fluid in (bio-) lubri.cants.
[0019] Preferably, said resulting oil (or said blend
of oil) further comprises more than (about) 72%, 75%, 80%, or
85% of oleic acid, and/or less than (about) 4%, 3,5%, 3%, 2%,
1% or 0, 5 0 of linolenic acid, based upon the total weight of
the fatty acids present in said oil.
[0020] The ratio rapeseed oil to oleaginous oil (more
particularly sunflower oil) can vary from 5/95 to 95/5, and
is preferably comprised between 50/50 to 95/5, any ratio
between these extremes being envisaged for a (bio-)lubricant
according to the invention.
[0021] The present invention also relates to the use
of a mono-alkyl esters composition derived from (or resulting
from the transesterification of) rapeseed oil as a base fluid
in (bio-) lubricants. More particularly, said composition
comprises less than (about) 7%, 6,5%, 6% or 5,5% of mono-
alkyl esters of saturated fatty acids, based upon the total
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weight of the mono-alkyl esters of fatty acids present in
said composition.
[0022] Preferably, said mono-alkyl esters composition
further comprises more than (about) 72%, 75%, 80%, or 85% of
mono-alkyl ester of oleic acid, and/or less than (about) 4%,
3,5%, 3%, 2%, or 1% of mono-alkyl ester of linolenic acid,
based upon the total weight of the mono-alkyl ester of fatty
acids present in said composition.
[0023] Another object of the invention is the use of a
mono-alkyl esters composition derived from (or resulting from
the transesterification of) rapeseed oil and another
oleaginous oil. More particularly, said composition comprises
less than (about) 7%, 6,5%, 6% or 5,5% of mono-alkyl esters
of saturated fatty acids, based upon the total weight of the
mono-alkyl esters of fatty acids present in said composition,
as a base-fluid in (bio-)lubricants.
[0024] Preferably, said mono-alkyl esters composition
derived from said rapeseed and oleaginous oils further
comprises more than (about) 72%, 75%, 80%, or 85% of mono-
alkyl ester of oleic acid, and/or less than (about) 4%, 3,5%,
3%, 2%, 1% or 0,5% of mono-alkyl ester of linolenic acid,
based upon the total weight of the mono-alkyl ester of fatty
acids present in said composition.
[0025] The additives used in a (bio-)lubricant
according to the invention can be bactericides, fonggicides,,
metal deactivators, friction reducers, viscosity modifiers,
antioxidants, antiwear agents, anti-scuff agents, pourpoint
depressants, rust inhibitors, dispersants, detergents, and/or
antifoam agents, etc.
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[0026] Said rapeseed oil is preferably extracted from
one, two or more of the following varieties: CARACAS,
CONTACT, CABRIOLET, CALIDA, SPIRAL, MSP05, MSP11 and MSP13.
[0027] Said other oleaginous oil is preferably
extracted from sunflower. Preferably the oil is extracted
from AURASOL and/or ELANSOL varieties seeds.
Detailed description of the invention
[0028] The present invention provides a new
(bio-) lubricant comprising (or consisting of) a rapeseed oil
and at least one additive, wherein the saturated fatty acids
content of said rapeseed oil is less than (about) 7%, 6,5%,
60 or 5,5%, preferably between (about) 7% and (about) 5%,
more preferably between (about) 7% and (about) 5,5%, based
upon the total weight of the fatty acids present in the
rapeseed oil.
[0029] Another object of the present invention relates
to the use of a rapeseed oil as a base fluid for the
preparation of a (bio-) lubricant, wherein said rapeseed oil
comprises less than (about) 7%, 6,5%, 6 0 or 5, 5 0, preferably
between ( about ) 7% and ( about ) 5%, more preferably between
(about) 7% and (about) 5,50 of saturated fatty acids, based
upon the total weight of the fatty acids present in the
rapeseed oil.
[0030] Preferably, said rapeseed oil further comprises
more than (about) 72%, 75%, 80%, 81%, 82%, 83%, 84%, 85%,
86%, 87%, 88%, 89% or 90 0, preferably between (about) 70% and
(about) 90%, more preferably between (about) 72% and (about)
89% of oleic acid, and/or less than (about) 4%, 3, 5 0, 3%, 2%,
or 1%, preferably between (about) 4% and (about) 1% of
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linolenic acid, based upon the total weight of the f atty
acids present in the rapeseed oil.
[0031] More preferably, said rapeseed oil comprises
more than (about) 72%, 75%, 80%, or 85%, preferably between
(about) 72% and (about) 89% of oleic acid, less than (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 0, 6% or 5, 5 0, preferably between ( about ) 7% and ( about )
5%, more pre f erably between.( about ) 7% and ( about ) 5, 5% of
saturated fatty acids, based on the total weight of fatty
acids in the oil.
[0032] Said rapeseed oil may further comprise less
than 15%, 14%, 13%, 12%, 11%, 10%, 9% or 8%, preferably less
than about 7% or 6% of linoleic acid, and/or 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.
[0033] In said rapeseed oil, said saturated fatty
acids may comprise less than 4,5%, preferably less than about
4%, more preferably less than about 3,50 of palmitic acid
based upon the total weight of fatty acids present in the
oil. More particularly, said saturated fatty acids can
comprise between about 4,5o 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.
[0034] 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%, 6,80, 6,9%, 7,1%, 7,20, 7,3o and any real
number comprised between 6,7% and 7,3%.
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[0035] In the context of the present invention, the
term "base-fluid" refers to a lubricating fluid whose
properties, in particular its flow, ageing, lubricity and
antiwear properties as well as its properties regarding
contaminant suspension, have not been improved by the
inclusion of additives.
[0036] The additives used in a (bio-)lubricant
according to the invention (or in a process of the invention)
can be bactericides, fongicides, metal deactivators, friction
reducers, viscosity modifiers, antioxidants, antiwear agents,
anti-scuff agents, pourpoint depressants, rust inhibitors,
dispersants, detergents, and/or antifoam agents, etc.,
[0037] Depending on the effect sought and on, the.
additive(s) used, a (bio-)lubricant according to the
invention comprises preferably less than (about) 20 wt.%,
more preferably less than (about) 10 wt.%, and even more
preferably less than (about) 5 wt.% of additive(s), based on
the total weight of the (bio-)lubricant.
[0038] For example, a few ppm of silicone is commonly
used as foam inhibitor. Silicone can be used also to reduce
surface tension.
[0039] Examples of oxidation inhibitor additives that
can be used are zinc dithiophosphates, aromatic amines, alkyl
sulfides, hindered phenols, etc. In particular, BHA
(butylated hydroxyanisole) and/or BHT (butylated
hydroxytoluene) can be used, in an amount which is less than
( about ) 1 wt. o .
[0040] Typical anti-rust compounds are e.g. highly
basic compounds, sulfonates, phosphates, organic acids,
esters or amines.
[0041] Detergents and dispersants can be used in a
(bio-)lubricant of the invention for keeping sludge, fine
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solid, and semi-solid contaminants dispersed in the oil
(preventing deposits). Examples are compounds such as
succinimides, neutral calcium and barium sulfonates,
phenates, polymeric detergents and amine compounds. They can
also be basic calcium sulfonates / phenates which neutralize
sludge precursors.
[0042] Examples of anti-friction agents that can be
used are long chain (greater than 12 carbon atoms) alcohols,
amines and/or fatty acids (in particular oleic acid).
[0043] Antiwear agents are for example zinc
dialkyldithiophosphates (ZDDP) (the most commonly used),
carbamates, organic phosphates such as tricresyl phosphates,
organic phosphates, chlorine compounds, etc.
[0044] Common anti-scuff additives are e.g. sulphur or
phosphorous compounds more chemically active than anti-wear
additives. Common gear oil anti-scuff additive is a mixture
of an organic sulphur compound and an organic phosphorous
compound usually identified as S/P.
[0045] Examples of pour point depressants are
ethylene-vinyl-acetate- copolymers, vinyl-acetate-olefin
copolymers, alkyl-esters of styrene-maleic-anhydride
copolymers, alkyl-esters of unsaturated-carboxylic acids,
polyalkylacrylates, polyalkylmethacrylates, alkyl phenols,
and/or alpha-olefin copolymers, more particularly polyacylate
compounds and/or synthetic polyalphaolefin (PAO). They are
usually added in an amount less than (about) 5 wt.%,
preferably less than (about) 1 wt.%, typically between
( about ) 0,1 wt. o and ( about ) 0,5 wt.%.
[0046] A rapeseed oil can be extracted from Brassica
napus, Brassica rapa, Brassica carinata and/or Brassica
juncea seeds varieties.
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[0047] Preferably, said rapeseed oil is extracted from
the seeds of Brassica napus CV oleifera Metzger.
[0048] 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.
[0049] MSP11 variety is maintained as a Budapest
Treaty patent deposit with NCIMB under accession number NCIMB
41234 made July 9, 2004.
[0050] MSP13 variety is maintained as a Budapest
Treaty patent deposit with NCIMB under accession number NCIMB
41237 made July 23, 2004.
[0051] 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.
[0052] A mixture of the oil extracted from two, three,
four, five or six of these varieties can also be used to
prepare a (bio-)lubricant according to the invention.
[0053] 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.
[0054] 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.
[0055] 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
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acids, based upon the total weight of fatty acids present in
the oil.
[0056] 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.
[0057] A variety from which such oil can be extracted
may be chosen from the group consisting of MSP05, MSP11 and
MSP13 varieties.
[0058] A more preferred rapeseed oil comprises more
than about 80% of oleic acid and less than about 2% 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.
[0059] 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.
[0060] A variety from which such oil can be extracted
is for example MSP11 variety or MSP13 variety.
[0061] Another object of the invention relates to a
new (bio-)lubricant comprising (or consisting of) a rapeseed
oil and another oleaginous oil (more particularly sunflower
oil) and at least one additive, wherein the saturated fatty
acids content of the resulting oil is less than (about) 7%,
6,5%, 6% or 5,5%, preferably between (about) 7% and (about)
50, more preferably between (about) 7o and (about) 5,50,
based upon the total weight of the fatty acids present in the
rapeseed oil
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[0062] Another object of the invention relates to the
use of (a blend of) rapeseed oil and another oleaginous oil
(in particular sunflower oil) as base fluid in a
(bio-)lubricant, wherein the ratio of rapeseed oil to said
other oleaginous oil is selected so that a blend of both oils
(the resulting oil) comprises less than (about) 7 0, 6, 5 0, 6 0
or 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
blend.
[0063] Preferably the ratio of rapeseed oil to said
other oleaginous oil (more particularly sunflower oil) is
selected so that a blend of both oils further comprises at
least (about) 72%, 75%, 80%, 81%, 82%, 830, 84%, 85%, 860,
87%, 88%, 89% or 90%, preferably between (about) 72% and
( about ) 9 0 0, more preferably between ( about ) 75% and ( about )
89% of oleic acid and/or less than (about) 4%, 3, 5 0, 3%, 2%,
1,5% 1% or 0,5%, preferably between (about) 4% and 0,2% of
linolenic acid, based on the total weight of fatty acids in
the blend.
[0064] Preferably the ratio of rapeseed oil to said
other oleaginous oil (more particularly sunflower oil) is
selected so that a blend of both oils further comprises less
than 4,5%, preferably less than (about) 40, more preferably
less than (about) 3,5%, more preferably between (about) 40
and (about) 3%, of palmitic acid based upon the total weight
of fatty acids present in the blend.
[0065] Preferably the ratio of rapeseed oil to said
other oleaginous oil (more particularly sunflower oil) is
selected so that a blend of both oils further comprises less
than (about) 20%, 19%, 18%, 17% or 16%, more preferably less
than (about) 7,5% of poly-unsaturated fatty acids, based on
the total weight of fatty acids in the blend.
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[0066] The present invention also provides a new
(bio-)lubricant comprising (or consisting of) a mono-alkyl
esters composition derived from a rapeseed oil and at least
one additive, said composition comprising less than (about)
7%, 6, 5 0, 60 or 5, 5%, preferably between (about) 7% or 6% and
(about) 50, more preferably between (about) 7% or 6% 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 mono-alkyl esters composition.
[0067] Another object of the present invention is the
use as a base fluid of a mono-alkyl esters composition
derived from a rapeseed oil, said composition comprising less
than (about) 7%, 6,5%, 6% or 5,5%, preferably between (about)
7% or 6% and (about) 5%, more preferably between (about) 70
or 6% 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 mono-alkyl esters
composition.
[0068] Preferably, said mono-alkyl esters composition
derived from a rapeseed oil further comprises more than
(about) 72%, 75%, 80%, or 85%, preferably between (about) 70%
and (about) 90%, more preferably between (about) 75% and
(about) 85% of mono-alkyl ester of oleic acid and/or not more
than (about) 4%, 3,5%, 3%, 2%, 1,5%, 1% or 0,5% preferably
between (about) 4% and 0, 2 0 of mono-alkyl ester of linolenic
acid, based on the total weight of mono-alkyl ester of fatty
acids in the mono-alkyl esters composition.
[0069] Preferably, said mono-alkyl esters composition
derived from said rapeseed further comprises less than about
15%, 14%, 13%, 12%, 11%, 10%, 9% or 8%, preferably less than
about 7% or 6% of mon.o-alkyl ester (s) of linoleic acid,
and/or less than about 20%, 19%, 18%, 17% or 16%, preferably
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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.
[0070] Preferably, the mono-alkyl esters of said
saturated fatty acids comprise less than 4,50, 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.
[0071] Preferably, 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.
[0072] The present invention also provides a new
(bio-)lubricant comprising (or consisting of) a mono-alkyl
esters composition derived from rapeseed oil and another
oleaginous oil (more particularly sunflower oil) and at least
one additive, said composition comprising less than (about)
7%, 6,5%, 6% or 5,5%, preferably between (about) 7% or 6o and
(about) 5%, more preferably between (about) 7% or 6o 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 mono-alkyl esters composition.
[0073] Another object of the invention relates to the
use of a mono-alkyl esters composition derived from rapeseed
oil and another oleaginous oil (more particularly sunflower
oil) as base fluid in a (bio-)lubricant composition, said
composition comprising less than (about) 70, 6,5%, 6% or 5o,
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 mono-alkyl esters in said
composition.
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[0074] Preferably, said mono-alkyl esters composition
derived from rapeseed oil and said other oleaginous oil (more
particularly sunflower oil) further comprises more than
(about) 72%, 75%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%,
88%, 89%, 90%, preferably between (about) 72% and (about)
90%, more preferably between (about) 75% and (about) 85% of
mono-alkyl ester of oleic acid and/or less than (about) 4%,
3, 5 0, 3%, 2%, 1,5%, 1% or 0,5% preferably between (about) 410
and 0,2% of mono-alkyl ester of linolenic acid, based on the
total weight of mono-alkyl ester of fatty acids in said mono-
alkyl esters composition.
[0075] Preferably, said mono-alkyl esters composition
derived from said rapeseed and oleaginous oils (more
particularly sunflower oil) further comprises 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.
[0076] 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.
[0077] In a preferred composition of the invention,
the mono-a1ky1 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.
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[00781 Said mono-alkyl esters composition can result
from the transesterification of a blend of rapeseed oil and
said other oleaginous oil (more particularly sunflower oil),
wherein the ratio of rapeseed oil to said other oleaginous
oil (more particularly sunflower oil) is selected so that a
blend of both oils comprises less than (about) 7%, 6,5%, 6%
or 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
blend.
[0079] Alternatively, said mono-alkyl esters
composition can result from the transesterification of each
oil separately, the transesterified oils being mixed
afterwards, wherein the ratio of rapeseed oil to said other
oleaginous oil (more particularly sunflower oil) is selected
so that a blend of both oils would comprise (if they were
mixed) less than (about) 7%, 6,5%, 6% or 5%, preferably
between (about) 7% and (about) 5%, more preferably between
(about) 7o and (about) 5,5% of saturated fatty acids, based
on the total weight of f atty acids in the blend.
[00801 Preferably the ratio of rapeseed oil to said
other oleaginous oil (more particularly sunflower oil) is
selected so that a blend of both oils further comprises (or
would further comprise) more than (about) 72%, 75%, 80 0, 81%,
82%, 83%, 84%, 850, 86%, 87%, 88%, 89% or 90%, preferably
between (about) 70% and (about) 90%, more preferably between
(about) 75% and (about) 85% of oleic acid and/or less than
(about) 4%, 3, 5 0, 3 0, 2%, 1, 5 0, 1%, or 0,5%, preferably
between (about) 4% and 0,2% of linolenic acid, based on the
total weight of fatty acids in the blend.
[0081] Preferably the ratio of rapeseed oil to said
other oleaginous oil (more particularly sunflower oil) is
selected so that a blend of both oils (would) further
CA 02612836 2007-12-19
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17
comprise(s) less than 4,5%, preferably less than (about) 4%,
more preferably less than (about) 3,5%, more preferably
between (about) 4% and (about) 3%, of palmitic acid based
upon the total weight of fatty acids present in the blend.
[0082] Preferably the ratio of rapeseed oil to said
other oleaginous oil (more particularly sunflower oil) is
selected so that a blend of both oils (would) further
comprise(s) less than (about) 20%, 19%, 18%, 17% or 16%, more
preferably less than (about) 7,5% of poly-unsaturated fatty
acids, based on the total weight of fatty acids`in the blend.
[0083] The mono-alkyl esters of fatty acids in the
mono-alkyl esters compositions (derived from rapeseed oil
and/or said other oleaginous oil), used in a (bio-) lubricant
according to the invention, 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.
[0084] Preferably, 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.
[0085] It is to be understood that a (bio-) lubricant
of the present invention comprises further fatty acids
(transesterified or not) that are characteristic of the
rapeseed oil used (extracted from one or more varieties) or
of the blend of rapeseed oil and said other oleaginous oil
used (possibly extracted from one or more species and/or
varieties).
[0086] Another object of the invention is a process
for preparing a (bio-)lubricant according to the present
invention comprising the step of (1) extracting the oil from
the seeds of rapeseed varieties such as CONTACT, CABRIOLET,
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18
CALIDA, MSP05, MSP11 and/or MSP13, and optionally from the
seeds of another oleaginous species, in particular from the
seed of sunflower varieties, such as ELANSOL or AURASOL, and
(2) the step of adding at least one additive selected from
the group consisting of bactericides, fungicides, metal
deactivators, friction reducers, viscosity modifiers (e.g.
viscosity index improvers), antioxidants, antiwear agents,
anti-scuff agents, pour point depressants, rust inhibitors,
dispersants, detergents, and antifoam agents.
[0087] Oi1 extraction methods are well known and can
be mechanical, via solvents (generally hexane), via enzymes
and/or by means of high pressure CO2.
[0088] Preferably, a process of the invention further
comprises the step of degumming the crude oil.
[0089] Crude oil is degummed to remove bulk of certain
phosphatides such as lecithin.
[0090] The degumming treatment can consist of mixing
the oil with water or steam during a certain period of time,
preferably about 30 mi.n. to about 60 min., at a temperature
between about 50 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.
[0091] The degumming step may also consist of a
chemical process.
[0092] Preferably, a process of the invention further
comprises the step of refining the degummed oil.
[0093] The oil is refined (or neutralized) in order to
reduce the free fatty acids, phospholipids, carbohydrates or
proteins.
[0094] The most widely practiced form of refining
method is an alkali treatment, usually sodium hydroxide, by
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19
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.
[0095] After the alkali treatment, the oil is washed
with (hot) water to remove residual water soluble soaps that
can reduce stability of the oil. In addition, pigments of the
oil, such as chlorophyll, also undergo partial decomposition
during this step.
[0096] The refining step can also be referred to as a
neutralization step.
[0097] Preferably, a process of the invention further
comprises a bleaching step,.after the refining step.
[0098] 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.
[0099] 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.
[00100] A process for preparing a (bio-)lubricant
according to the present invention can further comprise the
transesterification step of the oil.
[00101] Said transesterification step may consist of a
base catalysed transesterifi.cati.on of the 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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[00102] The catalyst -is generally sodium hydroxide or
potassium hydroxide. It is generally dissolved in the
alcohol(s) using a standard agitator or mixer.
[00103] The alcohol(s) can be methanol, ethanol,
propanol and/or butanol. Excess alcohol is normally used to
ensure total conversion of the oil to its esters.
[00104] The alcohol(s) / catalyst mix is then charged
into a closed reaction vessel and the oil is added.
[00105] The system should be closed to the atmosphere
to prevent the loss of the alcohol (s) .
[00106] The reaction time may vary, generally 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.
[00107] 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.
[00108] 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.
[00109] 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.
[00110] The products of the reaction can be neutralized
before or after the two phases, containing respectively
glycerin and esters, are separated. This neutralization step
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21
can also take place before or after the alcohol(s) is (are)
removed in each phase.
[00111] The alkyl esters composition thus obtained can
be washed gently with warm water to remove residual catalyst
or soaps.
[00112] It can also be distilled in an additional step
to remove small amounts of colour bodies to produce a
colourless composition.
[00113] The glycerin by-product can be submitted to
further steps depending on the applications envisaged and the
degree of purity required.
[00114] 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.
[00115] In a more preferred embodiment, methanol is
used. And when methanol is used the transesterification step
can be referred to as a methanolyse step.
[00116] The transesterification may also consist of a
direct acid catalysed transesterification of the oil.
[00117] The alcohol can be methanol, ethanol, propanol
and/or butanol.
[00118] In a preferred embodiment, the alcohol used is
methanol, ethanol or a mixture of both.
[00119] Where methanol is used, the transesterification
step can also be referred to as a methanolyse step.
[00120] The transesterification may also consist of a
two steps reaction, the first being the conversion of the oil
to its fatty acids, and then the conversion of the fatty
acids to alkyl esters with acid catalysis.
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GG
[00121] The alcohol can be methanol, ethanol, propanol
and/or butanol.
[00122] 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.
[00123] Whatever are the catalysts used and/or the
alcohols used, the oil used in a process of the invention
comes from either rapeseed oil extracted from the seeds of
one or more varieties of rapeseed and exhibiting the features
mentioned in the present invention, or from rapeseed oil and
another oleaginous oil (more particularly sunflower oil), the
blend of which exhibits the features mentioned in the present
invention.
[00124] Said rapeseed oil and said other oleaginous oil
(preferably sunflower oil) can be submitted to the
transesterification step separately and the esters obtained
mixed afterwards. In that case, a process according to the
invention comprises the step of transesterification of each
(kind of) oil (from each variety, . from each species or from
each genus) and the step of mixing the alkyl-esters obtained.
[00125] Alternatively, said rapeseed oil and said
oleaginous oil (preferably sunflower oil) can be submitted to
the transesterification step as a blend of oil. In that case,
a process according to the invention comprises the step of
mixing the different oils and the step of transesterification
of the blend of oil.
[00126] The oils used as base-fluids and the
(bio-)lubricants obtained have been analysed to ensure they
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23
,meet the different specifications established by theEuropean
Union, the American Society for Testing and Materials (ASTM)
or other national or international instances.
[00127] 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.
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L4
0
m O
~ \y-cN N I o I I x~\ O Q4 0\0 F = N ~
bl ~
rn W ,-+
01 I :~l l- rl O U N
L(1 :zN -qN di l0 l0 rl Ol O 1.t1 \O N \~ L()
O 0 O rl pp N -I N l0 Ol N Cr) N O
0 110 H rI -I O CC) O l0 0 m O 0 c1 N
q co rn cn cn cn w
W N lo O 0 ~,o \ O
N O O O O O 0 H(a H H H H ~
H H H H H H ~ ~r4 ~r4 Z$ H
44
di Q
04
0
m O \
U co r~ ~4 O O t-~ N a
0 ,-I O ''~ 1~ N u U]
> Q x
a 0 4J
o a(d U ID O 0
~/ 0
CO cn H a a
U
U 0
0
a..)
0
O 0 tn
di H .o rl a)
0
O 4-.I r-I 4) N
a) .~ .U .!-s R~ ~O-I .
o O O'' ~ OIci G' ~
0 ~ u b O 0 0 O ~ ~ r-I
N -ri .!-> -rl (U rl .Q
41 > > H u ~4 ~ ~ ~ ~ ~
~ U U >4 r, 41 U U U ro 0 4-1
~ -H .u -rq (~ 0 F., -r-t > a) 4 -~
.u .U -rl 0 ~I (CS m 4-I 10 0
.!J rf1 fd U] a N.1_1 ~f =rl N =rI ci 0
~ =H F~ F~ O r-I U2 ifl 0 i x a a
H Ul 4) N U ~-1 Q) -H =rl 10 0 -rl 0 f1l
0 m ~ U m m - 1 a'~ O cn
-r-i -r-i O U (1) a) U m 0 a)
H Q x X > a r~ r~ cn H a a
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WO 2007/034336 PCT/IB2006/003847
[00128] A preferred oil to be used as base-fluid
comprises about 6% of saturated fatty acids based on the total
weight of the fatty acids present in the oil.
[00129] Preferably, said oil further comprises about 85%
of oleic acid based on the total weight of the fatty acids
present in the oil.
[00130] Preferably, said oil further comprises about 20
of linolenic acid based on the total weight of the fatty acids
present in the oil.
[00131] Preferably, said oil further comprises about 3, 5 0
of palmitic acid based on the total weight of the fatty acids
present in the oil.
[00132] Preferably, said oil further comprises about 7,5%
of poly-unsaturated acids based on the total weight of the
fatty acids present in the oil.
[00133] Said preferred oil to be used as base-fluid can
comprise (or consist of) an oil extracted from MSP11 seeds.
[00134] Said preferred oil (more particularly an oil
extracted from MSP11 seeds) can be mixed with an oil extracted
from another rapeseed varieties and/or from another oleaginous
(in particular from high oleic sunflower varieties) in a ratio
such that the resulting oil comprises between (about) 6,5% and
(about) 5%, more preferably between (about) 6% and (about) 5,5%
of saturated fatty acids, based on the total weight of the
fatty acids present in said resulting oil.
[00135] Preferably, said ratio is such that the resulting
oil further comprises between (about) 82% and (about) 89%, more
preferably between (about) 84% and (about) 87% of oleic acid,
and/or between (about) 2% and (about) 0,5%, more preferably
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26
between (about) 2% and (about) 1% of linolenic acid , based on
the total weight of the fatty acids present in said resulting
oil.
[00136] Preferably, said ratio is such that the resulting
oil further comprises between (about) 5% and (about) 9 %, more
preferably between (about) 6% and (about) 8% of poly-
unsaturated fatty acids, based on the total weight of the fatty
acids present in said resulting oil.
[00137] Preferably, said ratio is such that the resulting
oil further comprises between (about) 3% and (about) 4%, more
preferably about 3,5% of palmitic acid , based on the total
weight of the fatty acids present in said resulting oil.
[00138] More preferably, said ratio is such that the
resulting 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.
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27
EXAMPLES
Example 1: Oil extraction
a) . Mechanical extraction
[00139] The seeds are pressed in a single screw press,
TAby 40A press, with a diameter of 6,5 mm, at a temperature
comprised between about 401 and about 60 C.
[00140] The following varieties are pressed: CARACAS,
CONTACT, CABRIOLET, CALIDA, SPIRAL, MSP05, MSP11, MSP13,
ELANSOL and AURASOL varieties.
[00141] The result of that step is summarized in Table
II.
[00142] In this example and in the following examples,
the CARACAS variety is used as a point of reference.
[00143] 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
[00144] Extractor 5L, a thermic bath and an extraction
cartridge 13L.
Conditions of the extraction
[00145] 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.
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[00146] 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 900C, 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.
[00147] The results of the extraction steps are
summarized in Table III.
Example 2: Degurcaning step.
[00148] The degumming and the neutralization are both
carried out in 10 litres temperature controlled reaction
vessel.
[00149] In order to facilitate the degumming, mainly the
decantation, the residual hexane content is adjusted at 6%.
[00150] The degumming step aims to remove the
phospholipids naturally present in the crude oil.
[00151] The oil is introduced in the reaction vessel,
then the temperature is raised up to 65 C while the oil is
agitated. At 65 C, phosphoric acid (1,5-~o) 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,
the decantation is allowed to proceed during 30 min. Finally,
the heavier phase is removed.
[00152] The results of this step are summarized in Table
IV.
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29
Example 3: Refining or neutralization step.
[00153] This step aims to remove the free fatty acids
present in.the degummed oil.
[00154] 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.
[00155] 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.
[00156] Then the aqueous phase is withdrawn (pH of 11-12)
and the oil is washed with demineralized water until the used
water is neutral.
[00157] The oil is then dried at 110 C under vacuum
during 30 min.
[00158] The process and the results are summarized
respectively in Table V and Table VI.
[00159] 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.
[00160] With an acid number below 0,3 mg KOH/g, the
degumming and refining steps are regarded as very efficient.
Example 4: Bleaching step.
[00161] The refined oil is introduced in the reaction
vessel with 3%, based on the weight of the oil, of TONSIL
earth.
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[00162] 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.
[00163] 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
carried out on a filter ("cloche" filter), at a flow rate of
about 20L/h.
[00164] The oil is then cooled down with the ambient
temperature during 1 hour and stored under nitrogen atmosphere.
[00165] The results of the bleaching step are summarized
in Table VII.
[00166] 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.
[00167] The fatty acids content of the oils extracted
from the different rapeseed and sunflower varieties have been
evaluated by gas chromatography and the results are summarized
in Table VIII.
Example 6: Methanolyse.
[00168] Approxi.mately 2000 g of oil extracted from
rapeseed seeds.
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31
[00169] The oil is degummed and refined according to the
process described in examples 2 and 3, and then mixed with 300
g of methanol in a reaction vessel. About 5 to 10 g of sodium
hydroxide added to the same reaction vessel.
[00170] The methanolyse takes place during about 2 hours,
at a temperature comprised between approximately 40 C and 60
C, under atmospheric pressure.
[00171] These conditions provide essentially about 95 o
conversion of added triglycerides to fatty acids methyl esters.
[00172] 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
in the lower phase. The upper phase is used in a second
conversion.
[00173] 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
pressure are applied (between about 40 and 60 C, atmospheric
pressure). In these conditions more than 98 % of triglycerides
are converted to fatty acids methyl esters.
[00174] The fatty acids methyl esters are washed and
dried. More than 1900 g of fatty acids methyl esters are
weighted, with a purity of higher than 98%. The mass yield,
methyl esters / refined oil, is good.
[00175] The methyl esters content of the methyl ester
composition obtained by the process as described has been
evaluated by gas chromatography and the results are summarized
in Table IX.
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32
Example 7: Test of hydrolyse resistance.
[00176] A copper strip is dipped into a mixture of oil
and water contained in a glass bottle. The bottle is placed in
an oven at about 93 C (+/- 0,5 C) during about 48 hours, with a
rotation of about 5 rev/min.
[00177] The mixture is then filtrated and the acidity
measured.
[00178] In parallel, the copper strip is examined having
regard to its mass and colour. A mark (or scoring) of less than
2B means that there is no corrosion ("2C" indicates the
occurrence of corrosion).
[00179] The conditions of the test are summarized in
Table X and the results obtained for different oils are
summarized in Table XI.
Example 8: JDQ16 method.
[00180] The mass, viscosity and acid number of the oil to
be examined are measured.
[00181] The oil is then placed into an oven at (about)
150 C during (about) 100 hours.
[00182] After this treatment, mass, viscosity and acid
number are measured again.
[00183] The changes of mass, viscosity and acid number of
the oil can thus be determined.
[00184] The results obtained can be compared to standard
transmission and hydraulic oils. They are summarized in Table
XII (for different rapeseed oils and sunflower oils) and also
in Tables XXI to XXVII (for different blends of different oils
in different ratios).
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33
Example 9: Specifications of different oils for use as base-
fluids in (bio-)lubricants.
[00185] The rapeseed oils and sunflower oils have been
analyzed and compared with the specifications of a
(bio-)lubricant as established by the European Union. The
results of such analysis are summed up in Table XIII.
[00186] The results obtained for different blends of
different oils (in different ratios) are summarized in Tables
XIV to XX.
CA 02612836 2007-12-19
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34
0
~n
~ O 00 N cN >1
Ol w U2
~ 61 l~ I I M N RS
F[ rI rI L~ 0 N -I W
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a Ol 00 M N fd
W r-I ,-i 00 o 00 r-i W
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r-I Ln M p- o >y
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CA 02612836 2007-12-19
WO 2007/034336 PCT/IB2006/003847
o r,,
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CA 02612836 2007-12-19
WO 2007/034336 PCT/IB2006/003847
36
0
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CA 02612836 2007-12-19
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o\o n Lf) Ln l0 L11 m c~ o l0
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+ H al . O rl . p ` H Ln
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CA 02612836 2007-12-19
WO 2007/034336 PCT/IB2006/003847
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o\
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-- 61 . O ~- p~ ` rl t.f)
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rv) (3)
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CA 02612836 2007-12-19
WO 2007/034336 PCT/IB2006/003847
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o\o trl
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01 Ol (\7 (y O. ~ O 00 N N 01 C) Ol rl l0 Vi O
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o\0 1
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CA 02612836 2007-12-19
WO 2007/034336 PCT/IB2006/003847
49
o\ u n Ln 'j, r- ~N 00 O
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CA 02612836 2007-12-19
WO 2007/034336 PCT/IB2006/003847
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CA 02612836 2007-12-19
WO 2007/034336 PCT/IB2006/003847
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CA 02612836 2007-12-19
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CA 02612836 2007-12-19
WO 2007/034336 PCT/IB2006/003847
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CA 02612836 2007-12-19
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CA 02612836 2007-12-19
WO 2007/034336 PCT/IB2006/003847
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