-1
PROCESS OF REACTIVE TRITURATION DIRECTLY ON AN OIL CAKE
Description
The present invention relates to a process for the reactive trituration of an
5 oil cake, to extract fatty acid esters therefrom.
An "oil cake" is a solid residue generally obtained from a process of
pressing oil-yielding plant seeds to recover oil (known as first cold-pressing or
hot-pressing oil). The cake may also be derived from a "double-pressing"
process, comprising a first pressing of the oil-yielding seeds followed by a
10 second step of pressing of the cake produced during the preceding step. The oil
cake may contain from 3% to 30% oil.
The oil recovered from the seeds of oil-yielding plants is for food, energy
or industrial use. The pressing of the seeds of oil-yielding plants, such as
rapeseed and sunflower, developed especially to provide oil for use as a fuel.
15 This oil production is accompanied by a large production of oil cakes,
which it is necessary to upgrade as best as possible, in order to optimize the
overall economic balance for this transformation.
Certain oil cakes, of rapeseed and of soybean, for example, may be of
interest in livestock rearing for animal nutrition. However, "de-oiled" cakes are
20 generally used, containing less than 3% oil. Their nutritional value is more
advantageous, their protein content is higher and their fat content is lower than
for oil cakes. Furthermore, oil cakes have a tendency to turn rancid, which
reduces the animal's appetite for this type of food.
It is known practice to extract the remaining oil of oil cakes by counter-
25 current percolation of a solvent (such as hexane) heated to 40-60°C for 4 to
5 hours. The mixture of oil and solvent then needs to be distilled in order to
separate them by heating to 115-120''C under suction and injection of steam.
The cakes thus "de-oiled" contain 0.5% to 2.5% oil. However, the steps of this
solvent-mediated oil extraction process are energy-intensive. Moreover, given
30 the highly volatile and flammable nature of hexane, these steps are classified as
hazardous and lead to a substantial release of volatile organic compounds into
the environment. The oil extracted from the cake is of mediocre quality
- 2 -
compared with the oil of first cold-pressing, and must be refined. This is
because the hexane-extracted oils are rich in undesirable compounds, such as
phospholipids. Furthermore, the acidity of the extracted oil is high, close to that
of the starting oil cakes, which themselves have a tendency to concentrate free
5 fatty acids. This acidity of the oil has the drawbacks of leading to the production
of soaps during the transesterification operations for the production of biodiesel,
but also of reducing the cold stability of the oil. The presence of free fatty acids
also complicates the refining process.
The oils thus extracted and refined are in some cases edible, and in
10 others only used in paint, in soap manufacture (by saponification of the oil), in
pharmacy and cosmetics, in industry and in oil chemistry for the production of
fatty acids, etc.
By transesterification of the oil in the presence of alcohol and a catalyst,
fatty acid esters used in biofuels are in particular manufactured. According to
15 the known techniques of the prior art, the manufacture of these esters from oil
cakes would thus require at least two main steps: extraction of oil from the cake
and then transesterification, these same steps being broken down into several
sub-steps.
The aim of the present invention is thus to provide a novel, simpler
20 process, which has the fewest possible steps, for upgrading oil cakes.
The Applicant has now found such a process for manufacturing in a
single step fatty acid esters from oil cakes.
One subject of the present invention is thus a process comprising at least
25 a step v) of reactive trituration which consists in placing an oil cake comprising
from 3% to 30% oil in contact with an anhydrous light alcohol and an alkaline
catalyst under temperature and time conditions that are sufficient to allow the
extraction and transesterification of the plant oil and that lead to the production
of a mixture comprising fatty acid esters and glycerol, and a de-oiled cake
30 comprising less than 3% oil.
The term "light alcohol" means a lower aliphatic alcohol in which the
number of carbons is within the range from 1 to 8, preferably from 1 to 5 or
better still from 1 to 4. The light alcohol is advantageously chosen from
methanol, ethanol, isopropanol, n-propanol, butanol, isobutanol and
2-ethylhexanol, and mixtures thereof. According to one preferred embodiment
of the invention, the light alcohol is methanol.
5 The alkaline catalyst used in the process is chosen from the group:
sodium hydroxide, alcoholic sodium hydroxide, solid sodium hydroxide,
potassium hydroxide, alcoholic potassium hydroxide, solid potassium hydroxide,
sodium or potassium methoxide, sodium or potassium ethoxide, sodium and
potassium propoxide, and sodium and potassium isopropoxide. According to
10 one preferred embodiment of the invention, the alkaline catalyst is sodium
hydroxide.
The oil cake used in the process of the invention is obtained from seeds
of any type of oil-yielding plant: almond, groundnut, safflower, hemp, rapeseed,
coconut, cotton, shea, flax, corn, mustard, rape, walnut, olive, cabbage palm,
15 poppy, castor-oil plant, jatropha, lesquerella, sea kale, camelina, sesame,
soybean and sunflower are examples thereof.
It would not constitute a departure from the context of the invention if the
cakes used in the process according to the invention were to originate totally or
partly from genetically modified oil-yielding plants.
20 Preferably, the oil cake has an acidity content that is in the range from 1
to 10 mg KOH/g, preferably from 1 to 8 mg KOH/g and preferably from 1 to
6 mg KOH/g, in order to avoid saponification reactions that reduce the ester
yield. This acidity of the oil cake is largely associated with the conditioning to
which the cake has been subjected after its production.
25 The oil cake is used alone or as a mixture with whole seeds (with their
husk), these seeds originating from the same plant or from another oil-yielding,
oil-protein-yielding or protein-yielding plant, said seeds preferably having an
acidity content of less than 3 mg KOH/g. These mixtures preferably comprise at
least 50% by weight of oil cake relative to the total weight of the mixture. These
30 mixtures have several advantages. First, they make it possible to reduce the
overall acidity content of the triturated material, since the cakes have a
tendency to be more acidic than the seeds from which they are derived. Now,
low acidity levels make it possible to improve the ester yield of the process.
Second, the addition of seeds with their husk makes it possible to curb the
lubricant effect of the oil cakes and improves the cohesion of the charge to be
treated, by creating by compression a sort of "stopper" that increases the
5 percolation and thus also improves the yield for the trituration reaction. The
compressed mixtures of cake and seeds may especially easily withstand
several percolation cycles during the trituration step v). These cake-seed
mixtures make it possible to increase the area of contact for better percolation
of the alcohol-catalyst mixture and thus better extraction of the lipids and their
10 consecutive transformation into esters.
For the purposes of the invention, the term "oil cake" means a cake that
contains 3% to 30% fat, or even rather 5% to 25% and preferably 7% to 20%
fat. In contrast with the "de-oiled cake" containing less than 3% fat, the oil cake
used in the present invention has not undergone extraction or washing with any
15 solvent.
In the present description of the invention, the terms "oil" and "fat" are
used independently to denote the lipids that are or are not extracted from the
cake.
The oil content of the oil cakes used in the present invention varies as a
20 function of the pressing conditions and of the seeds used. "Agricultural" oil
cakes and "industrial" oil cakes are generally distinguished. Pressing at a farm
is performed without a cooking pretreatment of the seeds, and the oil cakes
have a fat content that ranges from 12% to 30%. In the case of semiindustrial or
industrial installations, the pressing produces less fatty cakes, generally
25 according to one of the following two processes. In cold batch or continuous
pressing, the products are ground, crushed or flattened. The oil (especially olive
oil and walnut oil) is extracted by successive presses at a temperature below
80°C. The yield is low, the cakes conserving 6% to 12% fat. In continuous hot
pressing, the seeds are preheated up to 90°C, ground or flattened and then
30 pressed in an endless screw in which the temperature will be up to 120°C.
Another industrial variant consists in performing a second pressing step on the
^^R|
-5
cake obtained from the first seed pressing. The yield is improved. 4% to 20% oil
remains in the cake, depending on the seeds and the installations.
Advantageously, the reaction takes place in a fixed-bed reactor.
According to one embodiment, the fixed-bed reactor is a temperature-regulated
5 percolation column equipped with a grille. A pump feeds the column with
alcohol-basic catalyst mixture. The alcohol and the catalyst are thus added
simultaneously to the reactor, which is maintained at a temperature ranging
from 30 to 75°C, preferably less than or equal to 70°C, preferably less than
45°C, and preferably at about 40°C. The catalyst/alcohol/cake mass ratio is
10 preferably within the range 0.001 to 0.01/0.1 to 10/1 and preferably from 0.001
to 0.01/0.1 to 5/1, preferably in the range from 0.002 to 0.01/0.1 to 3/1 and even
more preferably in the range from 0.002 to 0.01/0.1 to 2/1.
In particular, a catalyst content of less than 0.001 or even less than 0.002
does not make it possible to obtain a sufficient yield of ester (i.e. a yield of at
15 least 50%) or a sufficient conversion of the triglycerides, diglycerides and
especially of the monoglycerides. Conversely, a content of greater than 0.01
leads to saponification and thus also to a poor yield of esters.
The introduction is performed at the top of the bed; the reaction liquid
then percolates through the bed and is recovered in a reserve located
20 downstream, under the bed. By pumping, the liquid is sent back to the top of the
bed to diffuse again in the bed. The duration of the recirculation cycle of the
alcohol/catalyst mixture is from 15 to 60 minutes and preferably from 20 to
40 minutes. At the end of the cycle, the liquid feed is stopped. Part of the liquid
that is still present in the soaked cake is then recovered by simple draining over
25 a period of 10 to 20 minutes. The recovered liquid may undergo a step of
neutralization by addition of acid, and then a step of evaporation of the alcohol,
to give a mixture of phases containing a lighter phase that is rich in esters and a
denser phase that is rich in glycerol. The phase mixture is subjected to a
decantation step (which consists, for example, of static decantation in one or
30 more decanters in parallel or in series, centrifugal decantation, or a combination
of static or centrifugal decantation), making it possible to obtain an upper phase
-6
predominantly composed of fatty acid esters (ester phase) and a lower phase
predominantly composed of glycerol and water (glycerol phase).
The ester phase is then subjected to a sequence of chemical reactions
and/or of separations/purifications directed towards recovering the fatty esters,
5 comprising, in a known manner, a step of washing with water followed by a step
of drying under vacuum.
The fatty acid ester thus obtained is intended especially for the
preparation of biodiesel.
The other product obtained directly from the process according to the
10 invention is the de-oiled cake. The de-oiled cake according to the invention
contains less than 3% oil, preferably less than 2%, or better still less than 1% by
weight of oil, relative to the weight of the cake.
The process according to the invention may without difficulty be
performed continuously at the industrial scale, for example using: a moving-
15 band reactor-extractor operating continuously (such as a De Smet extractor); a
rotary filter, a centrifuge or a centrifugal decanter. Preferably, the reactive
trituration is performed with methanol passing counter-currentwise through the
cake, over several consecutive stages.
According to one embodiment variant, an organic solvent (cosolvent) that
20 is miscible or immiscible with the said light alcohol is also added to the reaction
medium. In this case, the trituration step v) comprises the simultaneous
introduction into a reactor containing the said cake, of the anhydrous light
alcohol, of the basic catalyst and also of cosolvent. The latter is selected from
the following group: hexane, heptane, benzene, bicyclohexyl, cyclohexane,
25 decalin, decane, light spirit, petroleum ether, kerosene, kerdane, diesel oil, lamp
oil, methylcyclohexane, naphtha (Texsolve V), skellite, tetradecane, Texsolve
(B, C, H, S, S-2, S-66, S-LO, V), supercritical CO2, pressurized propane or
butane, natural solvents such as terpenes (limonene, alpha and beta pinene),
ethers such as dimethyl ether, diethyl ether, ketones such as acetone, and
30 mixtures of all these solvents.
Preferably, the light alcohol/cosolvent ratio is within the range from 10/90
to 90/10.
Advantageously, the process according to the invention also comprises,
before the trituration step v), at least one step ii) of pressing of oil-yielding plant
seeds to recover part of the oil of the seeds and to manufacture the said oil
cake. Any device and process known for this pressing step may be envisaged,
5 such as those already described above.
Optionally, the pressing step ii) is preceded by at least one of the
following steps i): crushing, hulling, preheating and/or drying of the seeds.
The term "crushing" of the seeds means a coarse reduction of the size of
the seed, which, as a function of its initial size, may be divided into two or more
10 parts that are more or less fine. This operation may be performed, for example,
on a corrugated-roll flattener or on a pin mill or a knife mill.
The term "hulling" of the seeds means the separation of the constituents
of the seed that are the kernel and the silverskin surrounding It. This operation
contributes towards ridding the seed of a non-oily constituent, the silverskin,
15 thus simultaneously making it possible to increase the oil productivity of the
process and also the protein content of the cake.
The term "preheating" of the seeds means a hot thermal treatment at a
temperature within the range from 50 to 90°C and preferably from 70 to SOX of
the seed, making it possible, depending on the desired objective:
20 - to increase the fluidity of the oil,
- to increase the plasticity of the seed to be pressed,
- to coagulate the proteins.
The term "drying" of the seeds means heating of the seed at a
temperature in the range from 60 to MO'C in order, depending on the desired
25 objective:
to adjust the moisture content of the seed to between 0.5% and 5%,
to destroy certain microorganisms (e.g. salmonella),
to deactivate the heat-sensitive enzymes (e.g. lipases),
to decompose the thermolabile toxic substances.
30 According to a preferred embodiment of the invention, to facilitate the
percolation of the solvent (based on anhydrous light alcohol and on alkaline
catalyst) through the three-dimensional lattice of the cake, the cake is "flaked"
#
before the reactive trituration step v). This flaking step iii) consists in crushing
the cake in order to destructure its three-dimensional, network without
evacuating fat from the cake.
Advantageously, the oil cake is dried (drying step iv)) before the reactive
5 trituration step v), preferably just after its manufacture, after step ii), for example
in a continuous hot-air dryer, at a temperature of between 60 and 140°C in
order to achieve a relative moisture content of less than or equal to 2%.
Preferably, less than 72 hours, preferably less than 48 hours, preferably less
than 24 hours and preferably less than 12 hours pass between step ii) of
10 manufacture of the oil cake and the reactive trituration step v). Advantageously,
the steps of the process according to the invention are performed continuously.
These preferred embodiments have the aim of performing the trituration step v)
on a "freshly prepared" oil cake, preventing it from becoming oxidized, hydrated
and hydrolyzed forming free fatty acids.
15 According to one advantageous embodiment of the process of the
invention, the cake is first flaked by simple flattening or multiple flattening, and
then dried before being used in reactive trituration performed in the presence or
absence of a cosolvent.
The process according to the invention makes it possible to react "in
20 planta" the light alcohol with the oil contained in the core of the cake. In this
process, the alcohol acts both as solvent and as reagent. The process
according to the invention makes it possible to pass directly from the cake to the
fatty acid esters, without prior extraction of the oil, avoiding the steps of refining,
purification and production of by-products such as bleaching earths normally
25 obtained during a filtration step, gums composed predominantly of
phospholipids, and/or soaps derived from refining (neutralization of the free fatty
acids).
The process of reactive trituration of the oil cakes according to the
invention leads to the simultaneous production of a de-oiled cake, glycerol and
30 fatty acid esters. For example, jatropha esters are obtained in the case of a
jatropha oil cake, or castor oil esters including ricinoleic acid ester in the case of
a castor-oil oil cake. The ricinoleic acid ester is intended mainly for the
lit
9-
manufacture of 11-aminoundecanoic acid, the constituent monomer of Rilsan®
11, which is a polyamide with exceptional physical properties, developed by the
Applicant. These esters are also suitable for the manufacture of biofuels.
The subject of the invention is especially a mixture of fatty acid esters,
5 especially of fatty acid methyl esters, which may be obtained via the process of
the invention, and which have a tocopherol content of greater than 10 mg/100 g.
These natural antioxidants present in plant oils impart better stability and better
resistance to oxidation of the mixture according to the invention. Furthermore, in
contrast with esters derived from a conventional extraction with hexane, which
10 must be refined in order to avoid the production of soaps, the fatty acid esters
according to the invention may be used directly, for example as biofuel, without
a prior refining step.
According to one embodiment variant, the alcohol-soaked de-oiled cake
is dried in a ventilated oven for 4 hours at a temperature of less than or equal to
15 200°C, preferably less than or equal to 150°C and even more preferentially less
than or equal to 120°C. This drying step makes it possible to remove from the
cake the solvent (alcohol) used during the extraction. This drying step also
makes it possible to destroy any toxins and allergens that may be remaining in
the cake.
20 According to another embodiment variant, the process according to the
invention does not comprise a step of drying the cake at high temperature
(temperature above 120°C); according to the conditions used, any toxins and
allergens may be inactivated by means of the physical and/or chemical
treatments applied to the oil cakes during the steps of the process of the
25 invention described above, such that the operation of drying of the cake at high
temperatures becomes unnecessary. In this case, the process comprises only
one step of drying of the cake at temperatures below 120°C, which is intended
to remove the solvent (alcohol) used during the extraction, in order to allow the
use of the said cake in animal feed.
30 Advantageously, the process according to the invention makes it possible
to obtain completely de-oiled cakes, which keep their physical integrity
10
(cohesion, mechanical strength) and which are detoxified and de-allergenized,
in which any toxins and allergens have been inactivated.
Phorbol esters, for example, are the main source of toxicity of Jatropha
cakes. This family of compounds is known for its harmful biological effects in
5 man and animals, especially in inflammation and the promotion of tumours.
Advantageously, the detoxified de-oiled cake(s) according to the invention have
a content of phorbol esters of less than or equal to 0.3 mg/g and preferably less
than 0.2 mg/g.
Among the inactivated toxins, examples that may also be mentioned
10 include ricin present in castor-oil oil cakes, or curcin present in jatropha oil
cakes. Among the allergens, mention may be made of the allergen CB-1A
present in castor-oil oil cakes. Assays of toxins, such as ricin, in the cake before
and after de-oiling show that the best cake detoxification results are obtained in
the case of the process according to the invention, by virtue of the simultaneous
15 presence of light alcohol and of alkaline catalyst. In contrast, the standard
extraction processes (unreactive trituration) on the cakes with solvent, for
example with hexane and/or methanol, always leave high contents of toxins in
the cake. The best detoxification results are obtained by reactive trituration
according to the invention using methanol and sodium hydroxide. It is noted in
20 particular that the light alcohol used alone (without cosolvent) in the presence of
alkaline catalyst gives better detoxification results than mixtures of light alcohol
with cosolvent (for example hexane) still in the presence of alkaline catalyst,
which themselves give better cake detoxification results than the standard
extraction processes without alkaline catalyst. It is thought that it is the alkaline
25 catalyst used in the present process that entails the noteworthy cake
detoxification effect. This effect is all the more observed when the starting cake
used in the process of the invention is less acidic. Specifically, in the case of
acidic oil cakes (acid number of greater than or equal to 10 mg KOH/g), the
alkaline catalyst rather has a tendency to neutralize the free fatty acids of the
30 cake to form soaps and cannot fully participate in the detoxification of the cake.
It
-11
10
The detoxified cakes according to the invention are of nutritional value and
may be used directly in animal feed, without constituting a risk to the health of
the persons handling them.
Besides food applications, the de-oiled cakes according to the invention
are rich in nitrogen and may also be used as fertilizer or as fuel. They may be
used as charcoal (after carbonization of the cake), optionally activated to make
active charcoal, as vegetable filler in biosourced composite materials, as biocarbon
used in agriculture, or alternatively for the manufacture of biogas, as a
source of nitrogen for microorganisms in methanization reactions to produce
energy in the form of methane.
The invention and its advantages will be understood more fully on reading
the examples below, which are given for purely illustrative and non-limiting
purposes.
20
25
Examples
Unless otherwise indicated, all the percentages are given on a weight basis.
In the examples below, the reactive trituration process according to the
invention is performed on cakes derived from an extraction step by mechanical
pressing.
Example 1: Reactive trituration test on a jatropha pressing cake
Preparation of the jatropha cake
Before pressing the jatropha seeds on a Taby 40A press, the jatropha seeds
are precrushed on a pin-roll flattener.
Table 1: Parameters of the mechanical pressing of the jatropha seeds
Materials
Tool
Die diameter, mm
Preheating of the seed
Parameters
single screw
12
yes
Comments
Taby press
semi-conical die
Temperature of 70
to SOX
»
12-
Table 2: Material balance for the mechanical pressing of the jatropha seeds
15
Material entering
Double-flattened jatropha seeds g
Volatile matter content, %RM**
Fat content, %DM*
IVIaterial exiting
Oil cake, g
Volatile matter content, %RM**
Fat content, %DM
Unfiltered raw pressing oil, kg
6848
7.5
35.0
4863
9.0
13.6
1985.1
20
*DM = dry matter
**RM = raw material
The cake prepared has a fat content of 13.6%. This cake is immediately dried at
100°C for 16 hours.
Example 2: Reactive trituration test on a jatropha pressing cake
The reactive trituration is performed in a percolation column equipped with a
fixed bed. It is performed under the following conditions:
1. The raw cake as exiting the press, of cylindrical form (length =
20 mm, diameter = 12 mm), is dried in an oven at 100°C for 16 hours.
Its relative moisture content is 0.8%.
2. The dried cake is introduced into the percolation column (350 g).
3. Methanolic sodium hydroxide solution at 0.4% relative to the cake is
then recirculated through the bed for 30 minutes at 50°C.
4. The miscella is then drawn off and the flake bed is then washed by
5 successive washes with methanol at 50°C (5 minutes per wash).
In view of the results of Table 3, it turns out that, under the test conditions, the
ester yield is 50%. This low yield is linked to a high saponifying activity (high
yield of glycerol, greater than 100% by weight since it contains other
compounds).
»
13
Table 3: Optimization of the catalyst content on thejatropha cake
TEST
Catalyst content (vs oil cake), %
Reaction and extraction temperature
Methanol/oil cake mass ratio
Yield of solids (1),%
Ester/glycerol phase separation
Ester yield, %
Glycerol yield, %
Cake ester potential, %
Fat content of the de-oiled cake, %DM*
Loss of ester (2), %
10-E36
0.4
50
1.6
94.5
yes
50.2
533
17.6
2.6
32.2
(1): The yield of solids is the ratio times 100 of the solids obtained after
evaporation of the miscella to the sum of the theoretical amounts of ester
and glycerol
(2) Loss of ester = 100 - ester yield - cake ester potential
*DM = dry matter
In qualitative terms (Table 4), the ester produced with 0.4% of catalyst engaged,
has moderate acidity and a moderate glyceride content.
10 Table 4: Analytical balance of the jatropha esters
Criterion
Acid number (mg KOH/g)
Monoglyceride content (%)
Diglyceride + triglyceride content (%)
10-E36
0.5
0.8
0.15
#
14-
In the presence of pressing cake, which is in the form of cylindrical pellets, it is
observed that the percolation rate of the methanolic sodium hydroxide solution
supplied in a [methanol/cake] ratio of 1.6 is very high.
This is why, in the following tests, it is sought to improve the lipids-methanolic
5 sodium hydroxide contact time and also the extractability of the fat by reducing
the [methanol/cake] ratio, but also by performing the test in the presence of
cosolvent (hexane in this case).
Example 3: Adaptation of the amounts of cosolvent and of catalyst
10 The reactive trituration is performed in a percolation column equipped with a
fixed bed. It is performed under the following conditions:
1) The crude cake as exiting the press, of cylindrical shape (length =
20 mm, diameter = 12 mm), is dried in an oven at 100X for 16 hours.
Its relative moisture content is 0.8%.
15 2) The dried cake is introduced into the percolation column (350 g).
3) The solution consisting of methanolic sodium hydroxide at 0.27%
(relative to the cake) and of hexane is then recirculated through the
bed for 30 minutes at 40°C.
4) The miscella is then drawn off and the flake bed is then washed by
20 5 successive washes with a mixture of methanol and hexane (in a
90/10 mass ratio at 40°C (5 minutes per wash)).
In test 10-E43 (Table 5 below), the reactive trituration temperature was reduced
by 10°C (50->40°C) in order to avoid evaporation of the hexane. Under the test
conditions (conditions adapted to the fat content of the cake) and by
25 comparison with the test without cosolvent, it appears that the ester yield for the
process according to the invention is improved (50-^58%), especially by virtue
of the presence of cosolvent.
30
#
- 1 5 -
Table 5: Material balance for the test performed in the presence of cosolvent
TEST
Fat content, %DM*
Catalyst content (vs oil cake), %
MeOH/hexane quality
MeOH/hexane/oil cake ratio
Yield of solids (1),%
Ester/glycerol phase separation
Ester yield, %
Glycerol yield, %
Cake ester potential, %
Fat content of the de-oiled cake, %DM*
Loss of ester (2), %
10-E43
13.6
0.27
90/10
0.72/0.08/1
85.0
yes
58.0
356
18.3
2.8
23.7
(1) The yield of solids is the ratio times 100 of the solids obtained after
evaporation of the miscella to the sum of the theoretical amounts of ester
and glycerol
(2) Loss of ester = 100 - ester yield - cake ester potential
(3) DM* = dry matter
Table 6: Analytical balance for the jatropha esters
Criterion
Acid number (mg KOH/g)
Monoglyceride content (%)
Diglyceride and triglyceride content (%)
IVIethod
EN14104
Arkema
Arkema
10-E43
nd
2.4
3.9
10
#
-16
Example 4: Adaptation of the amounts of cosolvent and of catalyst
In the following test, the amounts of hexane and of catalyst were increased to
increase the transesterifying activity.
The reactive trituration is performed in a percolation column equipped with a
5 fixed bed. It is performed under the following conditions:
1) The cake undergoes a preliminary operation of simple flattening on a
flattener equipped with smooth rolls (spacing of 0.05 mm) followed by
drying in an oven at lOO'C for 16 hours. Its relative humidity content
is 1.5%.
10 2) The dried cake is then introduced into the percolation column (350 g).
3) The solution consisting of methanolic sodium hydroxide at 0.7%
(relative to the cake) and of hexane (50/50 mass mixture) is then
recirculated through the bed for 30 minutes at 40°C.
4) The miscella is then drawn off and the flake bed is then washed by
15 5 successive washes with a mixture of methanol and hexane (in a
50/50 mass ratio at 40°C (5 minutes per wash)).
Under the conditions of test 10-E51 (see Table 7 below), the reactive trituration
temperature is still 40°C. Under these conditions, it is observed that the
increase in hexane content and in catalyst content has a positive effect on the
20 yield of esters (>80%) and also on the depletion of the cake (0.2% residual fat).
Table 7: Material balance for the reactive trituration test on flaked cake
performed at higher contents of hexane and of catalyst
TEST
Fat content of cake No. 2, %DM*
Oil acidity of the cake, mg KOH/g
Catalyst content (vs oil cake), %
Methanol/hexane/oil cake (flaked) ratio
Yield of solids (1), %
10-E51
18.7
6.0
0.7
1/1/1
110.4
^
-17
Ester/glycerol phase separation
Ester yield, %
Glycerol yield, %
Cake ester potential, %
Fat content of the de-oiled cake, %DM*
Loss of ester (2), %
yes
80.5
407.7
0.7
0.2
18.8
(1) The yield of solids is the ratio times 100 of the solids obtained after
evaporation of the miscella to the sum of the theoretical amounts of ester
and glycerol
(2) Loss of ester = 100 - ester yield - cake ester potential
(3) DM* = dry matter
Despite the acidity of the starting cake fat, which is initially high: 6 mg KOH/g,
the esters produced according to the process of the invention have moderate
acidity with an acid number of less than 0.5 mg KOH/g (Table 8).
Table 8: Analytical balance for the jatropha esters
Criterion
Acid number (mg KOH/g)
Monoglyceride content (%)
Diglyceride and triglyceride content (%)
IVIethod
EN14104
Arkema
Arkema
10-E51
0.46
1.1
0.2
10
Example 5: Detoxification of the jatropha cakes
Analytical technique:
To evaluate the detoxification of the cakes in the present description of the
15 invention, including in the examples, the preparation of the samples and the
assay of the phorbol esters were performed according to the method of Makkar
(Makkar HPS, Becker K, Sporer F, Wink M (1997) Studies on nutritive potential
and toxic constituents of different provenances of Jatropha curcas. J. Agric.
Food Chem. 45:3152-3157).
II
10
15
18
Preparation of the samples:
The liquid samples are diluted in methanol and then injected. For the solid
samples, the phorbol esters are first extracted with a mortar and pestle with
methanol, and the alcoholic extracts are then injected.
Operating conditions:
Detector: diode array (integration of the peaks at 280 nm).
Column: C18 reverse phase (LiChrospher 100, 5 |um), 250 x 4 mm +
precolumn.
Oven: 22°C (room temperature)
Eluents: B = acidified water (1.75 ml H3PO4 (85%) in 1 L of H2O)
A = acetonitrile
Table 9: Gradients
0 to 1 min
1 to 10 min
10 to 40 min
40 to 55 min
55 to 70 min
Acidified water
B (%)
60
50
25
0
0
Acetonitrile
A(%)
40
50
75
100
100
Flow rate: 1.3 ml/min.
Assay of the phorbol esters in the first pressing cake produced in Example 1:
20
19-
Table 10: Assay of the phorbol esters of ttie jatroptia cake
Seed engaged
(3)
Oil cake
Content of
phorbol
esters
mg/g
3.5
2.4
Distribution of
the phorbol
esters (as % of
PE of the seed)
100
50.1
The first-pressing cake still remains with a very high concentration of phorbol
esters (PE), i.e. the equivalent of 50% of the PEs of the starting seed.
5 Assay of the phorbol esters in the cake derived from the reactive trituration
process and produced in Example 4:
10
15
Table 11: Distribution ofttie phorbol esters in the reactive trituration test - Test
10E51 (reactive trituration test with 50/50 methanolAiexane cosolvent)
Cake(1)
Content
ofPE
mg/g
0.1
Distribution of the
PEs (as % of PEs
of the seed)
1.7
(1) Drying temperature = 100°C, 16 hours.
The cake obtained from the process according to the invention of reactive
trituration on a pressing cake with cosolvent is much more detoxified than that
obtained from a first-pressing process. Its content of phorbol esters (PE), i.e.
0.1 mg/g of cake, in effect corresponds to 1.7% of the PEs of the seed. The
reactive trituration process performed on a first-pressing cake is indeed a
detoxifying process.

(T- ^'-4:
20
1 2 U^:V^J i l '"
CLAIMS
10
15
20
1. Process comprising at least one reactive trituration step v) which
consists in placing an oil cake comprising from 3% to 30% oil in contact with an
anhydrous light alcohol and an alkaline catalyst under temperature and time
conditions that are sufficient to allow the extraction and transesterification of the
plant oil and leading to the production of a mixture comprising fatty acid esters
and glycerol, and a de-oiled cake comprising less than 3% oil.
2. Process according to Claim 1, in which the trituration step v)
comprises the simultaneous introduction into a reactor containing the said cake,
of anhydrous light alcohol, of basic catalyst and also of a cosolvent selected
from the group: hexane, heptane, benzene, bicyclohexyl, cyclohexane, decalin,
decane, light spirit, petroleum ether, kerosene, kerdane, diesel oil, lamp oil,
methylcyclohexane, naphtha (Texsolve V), skellite, tetradecane, Texsolve (B, C,
H, S, S-2, S-66, S-LO, V), supercritical CO2, pressurized propane or butane,
natural solvents such as terpenes (limonene, alpha and beta pinene), ethers
such as dimethyl ether or diethyl ether, ketones such as acetone, and mixtures
of all these solvents.
25
3. Process according to Claim 1 or 2, also comprising, before the
trituration step v), at least one step ii) of pressing of seeds of oil-yielding plants
to recover part of the oil from the seeds and to manufacture the said oil cake.
4. Process according to Claim 3, also comprising, before step ii), at
least one of the following steps i): crushing, hulling, preheating and/or drying of
the seeds at a temperature of less than or equal to 1G0°C.
30 5. Process according to any one of the preceding claims, also
comprising a step iii) of flaking the oil cake before the reactive trituration step v).
. ^ , i . , * ;;;;/iL f>^^0'tW1'5
21 \ 2 \\0 "i^^
6. Process according to any one of the preceding claims, also
comprising a step iv) of drying the oil cake at a temperature in the range from 60
to 140°C, before the reactive trituration step v).
5 7. Process according to any one of Claims 3 to 6, in which less than
72 hours, preferably less than 48 hours, preferably less than 24 hours and
preferably less than 12 hours pass between step ii) of manufacture of the oil
cake and the reactive trituration step v).
10 8. Process according to any one of Claims 3 to 7, in which the steps
are performed continuously.
9. Process according to any one of the preceding claims, in which
the oil cake has an acidity level of less than 10 mg KOH/g, preferably less than
15 5 mg KOH/g and preferably less than 2 mg KOH/g.
10. Process according to any one of the preceding claims, in which
the light alcohol is methanol.
20 11. Process according to any one of the preceding claims, in which
the alkaline catalyst is sodium hydroxide.
12. Process according to any one of the preceding claims, in which
the catalyst/alcohol/oil cake mass ratio is in the range 0.001 to 0.01/0.1 to 10/1,
25 preferably from 0.001 to 0.01/0.1 to 5/1, preferably in the range from 0.002 to
0.01/0.1 to 3/1 and even more preferably in the range from 0.002 to 0.01/0.1 to
2/1.
13. Process according to any one of Claims 2 to 12, in which the light
30 alcohol/cosolvent ratio is in the range from 10/90 to 90/10.
^ * ft.«'a-
22-
14. Process according to any one of the preceding claims, in which
the mixture comprising fatty acid esters and glycerol is subjected to a
decantation step to obtain an upper phase predominantly composed of fatty
acid esters and a lower phase predominantly composed of glycerol and water.
5
15. Process according to Claim 14, in which the said upper phase is
subjected to a succession of chemical reactions and/or of
separations/purifications leading to the production of biodiesel.
10 16. Process according to any one of the preceding claims, in which
the oil cake is obtained from the pressing of castor oil seeds and the said fatty
acid esters comprise ricinoleic acid ester.
17. Detoxified de-oiled cake which may be obtained via the process of
15 one of Claims 1 to 16, having a content of phorbol esters of less than or equal
to 0.3 mg/g and preferably less than 0.2 mg/g.
20
18. Use of the de-oiled cake according to Claim 17 in animal feed, as
fertilizer, as biocarbon, as biofuel, as fuel or as biogas.
19. Mixture of fatty acid esters, especially of fatty acid methyl esters,
which may be obtained via the process of any one of Claims 1 to 16, having a
tocopherol content of greater than 10 mg/100 g.
25 20. Use of the mixture according to Claim 19 as a biofuel.