Note: Descriptions are shown in the official language in which they were submitted.
CA 02466834 2004-04-28
WO 03/038020 PCT/CA02/01684
METHOD FOR FRACTIONATING GREASE TRAP WASTE AND
USES OF FRACTIONS THEREFROM
FIELD OF THE INVENTION
The present invention relates to the recycling of residual oils, fats and
greases as biofuels, in biodiesel formulations and other oleochemical
applications.
BACKGROUND OF THE INVENTION
Most commercial unsaturated acids (i.e. oleic acid) are derived from
animal tallow (by- product of the meat industry), tall oil (by-product of
paper mills)
or natural vegetable oils.
Fat splitting processes are well known in the art. The most common
methods are:
1) Twichell process;
2) Batch autoclave process;
3) Continuous process; and
4) Enzymatic process.
In Twichell process, the fat is hydrolyzed at a temperature of 100 C to
105 C and at atmospheric pressure for 12 to 48 hours. Alkyl-aryl acid or
cycloaliphatic sulfonic acid with sulfuric acid (0.75 - 1.25% w/w) are used as
CA 02466834 2004-04-28
WO 03/038020 PCT/CA02/01684
catalysts. Yields of 85% - 95% are obtained. The main inconvenients resulting
from this process are the catalyst handling, long reaction time, tendency to
form
dark-colored acid and high labor cost.
In the batch autoclave operations, the fat is hydrolyzed in the presence or
absence of a catalyst. Live steam is injected continuously at the bottom while
venting a small amount thereof to maintain the desired agitation and operating
pressure. After settling and formation of an aqueous and a fatty acid phase,
the
fatty acid phase is treated with mineral acid. The fatty acid phase is further
washed with water to remove traces of the mineral acid. Under catalytic
conditions (i.e. zinc, calcium or magnesium oxides) the fatty acid phase is
reacted for a period of 5 to 10 hours at 150 C - 175 C. A high yield of about
85%
- 95% is obtained. Without catalyst the fatty acids phase is reacted for a
period
of 2 to 4 hours at a high temperature (240 C) to give similar yields. The main
inconvenients resulting from this process are the catalyst handling and high
labor
cost.
In continuous operations also known as the Colgate - Emery process, a
single-stage countercurrent high pressure splitting is carried out for fat
hydrolysis.
The fat is introduced by means of a sparge ring from the bottom of the
splitting
tower while water is introduced by the top. The crude fat passes as a coherent
phase from the bottom to the top, while heavier splitting water travels
downward
as a dispersed phase through the mixture of fat and fatty acids. The high
temperatures involved (250 C - 260 C) associated to high pressures (725 psi)
assures degrees of splitting up to 98% in only 2 to 3 hours. The principal
inconvenients of this process are the high cost associated with the equipment
and the restriction to relative clean starting materials.
In enzymatic operations, the lipase from Candida rugosa, Aspergillus
niger, and Rhizopus arrhizus had been studied at temperatures of 26 C to 46 C
for periods of 48 to 72 hours. Even though 98% of splitting is claimed there
is no
2
CA 02466834 2004-04-28
WO 03/038020 PCT/CA02/01684
commercial process available until now. The principal inconvenient of this
process is that because enzymes work very well over a specific substrate under
specific conditions. Therefor, when the starting material is composed of more
than one product, the reaction is less selective. Long reaction times and
great
volumes required to satisfy the optimal concentration are also current
problems
involved in this kind of procedure.
Fractionation of free fatty acids is commonly performed by distillation of
tall
oil. Tall oil is recovered in most paper mills by acidulation of the soap
skimming
from black liquor. Crude tall oil (CTO) consists of a mixture of fatty acids
(40% -
45%), resin acid (40% - 45%) and various neutral components (i.e.
hydrocarbons, wax alcohols, sterols, esters and residues). About 40% to 50% of
the fatty acids contained in tall oil are oleic acid, while another 35% to 45%
are
linoleic acid. Higher quality of tall oil fatty acids, TOFA, (less than 2% of
resins
acid) can be obtained by distillation through two columns: a rosin column and
a
fatty acids column.
Oleic acid is probably the most important unsaturated fatty acids (UFA)
because many applications have been developed for its use in different fields
(i.e.
cosmetics, chemicals, lubricants, textiles, etc.). Separation of oleic acid
form tall
oil distillates requires additional refining steps. Best known-process for
fractionation of fatty acids by crystallization from solvent is the "Emersol"
process,
developed by Emery Industries Inc. in 1934. Different American patents used
different solvents (methanol: 2,421,157; acetone: 2,450,235 and methyl
formate:
3,755,389) to separate saturated fatty acids from unsaturated fatty acids. The
process was optimized by addition of crystallizing promoters (neutral fats,
tallow,
and glycerol tri-stearate). One more refined promoter is described in
Australian
patent AU-28434/92. It is the reaction product of: 1) a polyhydric alcohol
(i.e.
3
CA 02466834 2004-04-28
WO 03/038020 PCT/CA02/01684
glycerol, pentaerythritol, trimethylol pentane, etc.), 2) a dicarboxylic acid
(i.e.
adipic, oxalic, succinic, azelaic, glutaric and tartaric) and 3) a fatty acid.
All these processes require explosion proof installations and low
temperature refrigeration systems.
Other methods for producing oleic acid involve separation over molecular
sieves (US 4,529,551 and US 4,529,551); lithium soap separation (US
4,097,507), urea complexation (US 2,838,480 and US 4,601,856) and
complexation with dienophiles (US 5,194,640). All these process have the
inconvenient of a high cost operation associated to the use of chemicals
required.
Dry fractionation technology was originally developed for treatment of
animal fat (i.e. beef tallow) in the 60's. Since this time, many improvements
were
performed in response to the ever-increasing demand of the industry for new
products with very specific requirements. Two main sources are now the target
of
this technology: 1) vegetable oils such as palm oil, soybean oil, sunflower
oil,
rapeseed oil, groundnuts oil, cottonseed oil and palm kernel oil and 2) animal
fats
such as beef tallow, milk fat, lard and fish oil.
These fats and oils are mainly composed of triglycerides, diglycerides and
monoglycerides (i.e. a broad range of melting points) constituting a large
number
of intersoluble glycerides that are very difficult to separate by dry
fractionation
(i.e. solvent free crystallization). The separation of a liquid fraction (i.e.
olein,
used in food oil) and a solid fraction (i.e. stearin, used in shortening and
margarine) can be achieved through dry fractionation.
4
CA 02466834 2004-04-28
WO 03/038020 PCT/CA02/01684
In the present invention, dry fractionation was used to separate purified
free fatty acid obtained by splitting the residual oils and greases
recuperated from
industrial and commercial operations (i.e. trap greases, yellow greases and
brown greases).
The free fatty acids obtained from these starting materials are mainly
constituted by unsaturated fatty acids, such as mainly oleic acid, linoleic
acid,
linolenic acid and saturated fatty acids such as palmitic acid and stearic
acid. The
range of melting points for these limited numbers of products, in comparison
with
all the possible combinations presented by glycerides, was shown to be wide
enough to perform a highly selective separation.
Vegetable oils (i.e. triglycerides) were the first fuels used in diesel
engines.
They were subsequently abandoned because of major problems associated with
their use (i.e. injector fouling, ring sticking and varnish build-up on the
cylinder
walls). As it is known, these problems are the result of high viscosity and
high
reactivity of polyunsaturated fatty acids present in triglycerides.
More efficient and economical petroleum-based fuels rapidly shifted these
vegetable oils fuels. Today fuels are composed of mixtures of hydrocarbons
derived from mineral oils. However, it is well known that exhaust gases from
internal combustion of mineral fuels (CO, NOx, SOx, etc.) are shown to be very
polluting. Moreover, in view of the limited mineral oil reserves and their
increasing
cost, there is a demand for renewable fuels that could replace petrol
hydrocarbons or would permit the existing resources to be more effectively
used.
5
CA 02466834 2004-04-28
WO 03/038020 PCT/CA02/01684
Since the introduction of vegetable oil fuels (i.e. biodiesel) in the forties,
much work has proceeded to increase its viability as a fuel substitute. In
recent
years, there has been a considerable amount of research worldwide on
alternative diesel fuels. Biodiesel research programs, based on vegetable
oils,
are centered in eliminating the former problems (high viscosity and
reactivity), the
quality of emission, waste minimization and cost.
Viscosity problems were overcome by a drastic reduction of the molecular
weight of branched triglycerides into linear monoesters more similar to
straight
hydrocarbons in regular diesel. The procedure of conversion involves a
transesterification reaction with an alcohol. This reaction is preferably
carried out
in excess of alcohol (i.e. methanol or ethanol) and in the presence of a
catalyst
(i.e. sodium or potassium hydroxide). The products from the reaction are:
a) esters of vegetable oil;
b) glycerin;
c) alcohol (non-reacted excess) and
d) residual and spent catalyst.
At the end of the reaction, products are separated in two phases: an upper
non-polar ester rich phase and a lower polar glycerin phase. The non-reacted
alcohol and the residual and spent catalyst are distributed between the ester
and
glycerin phases. Moreover, some low molecular weight esters are dissolved in
the glycerin phase. As each one contaminates both phases, many attempts to
improve phase's separation have been developed.
6
CA 02466834 2004-04-28
WO 03/038020 PCT/CA02/01684
Low glycerin content in biofuels is required to avoid clogs of the injection
nozzles during combustion. Austria has been the first country to set a
national
biodiesel standard with maximum glycerin content (0.24% total and 0.02% free).
Actually these values are recognized in many countries including the American
National Biodiesel Board (NBB).
In the case of biodiesel fuel obtained from soy oil, 20% of crude glycerol is
produced as a by-product and that represents a major effluent problem. The
market for very high purity glycerol is limited and it requires very expensive
purification. To overcome effluent problems, development projects were focused
on different uses of the glycerol phase.
U.S. 5,145,563 (Culbreth et al., 1992) describes the use of ethers of
glycerol as extractive distillation agent.
U.S. 5,308,365 (Kesling et al., 1994) describes the use of glycerol ethers
mixed with biodiesel fuels to improve emissions content.
U.S. 5,476,971 (Gupta, 1995) describes reacting pure glycerol with
isobutylene in the presence of an acid catalyst in a two phases reaction to
produce mono-, di- and tri-tertiary butyl ethers of glycerol.
U.S. 5,413,634 (Shawl et al., 1995) describes use of ethers of glycerol as
an additive to enhance physical properties of cement.
7
CA 02466834 2004-04-28
WO 03/038020 PCT/CA02/01684
US patent 5,424,467 (Bam et al., 1997) described the use of glycerol as a
solvent for washing the ester phase to carry out the excess of methanol and
the
catalyst.
US patent 6,015,440 (Noureddini, 2000) describes the elimination of the
glycerin phase by converting it to ether derivatives by reacting glycerol with
isobutylene in order to obtain only one phase (alcohol esters & glycerol
ethers).
All these attempts to improve glycerol elimination and/or valorization
require additional costly steps. It is quite evident that even in view of
known prior
art, the presence of glycerol as a by-product of the transesterification of
triglycerides present in oils continues to be a problem.
Many of the problems related to the presence of glycerol could be
overcome by utilizing other starting material other than vegetable oils (i.e.
triglycerides).
Free fatty acids (FFA) obtained by fractionation of residual oils and
greases recovered from industrial and commercial operations (i.e. grease trap
waste: GTW) could be successfully used in the production of the aforementioned
biodiesel. However such products may exert a strong odor during its
processing.
8
CA 02466834 2004-04-28
WO 03/038020 PCT/CA02/01684
SUMMARY OF THE INVENTION
An object of the present invention is to provide an industrial application of
residual oils, fats and greases.
Another object of the present invention is to provide a process for the
production of Free Fatty Acids (FFA), from residual oils and greases
recuperated
from industrial and commercial operations (i.e. grease trap waste: GTW) that
overcomes most of the above-mentioned problems.
A further object of the present invention is to provide a process for the
production of Unsaturated Fatty Acids (UFA), from residual oils and greases
recuperated from industrial and commercial operations (i.e. grease trap waste:
GTW).
A further object of the present invention is to provide a process for the
production of Residue UFA, from residual oils and greases recuperated from
industrial and commercial operations (i.e. grease trap waste: GTW).
A further object of the present invention is to provide a process for the
production of Oleic Acid, from residual oils and greases recuperated from
industrial and commercial operations (i.e. grease trap waste: GTW).
A further object of the present invention is to provide a process for the
production of Saturated Fatty Acids (SFA), from residual oils and greases
recuperated from industrial and commercial operations (i.e. grease trap waste:
GTW).
A further object of the present invention is to provide a process for the
production of Residue SFA, from residual oils and greases recuperated from
industrial and commercial operations (i.e. grease trap waste: GTW).
9
CA 02466834 2004-04-28
WO 03/038020 PCT/CA02/01684
A further object of the present invention is to provide a process for the
production of Stearin, from residual oils and greases recuperated from
industrial
and commercial operations (i.e. grease trap waste: GTW).
A further object of the present invention is to provide a process for the
production of Purified stearin, from residual oils and greases recuperated
from
industrial and commercial operations (i.e. grease trap waste: GTW).
A further object of the present invention is to provide a process for the
production of biodiesel from residual oils and greases recuperated from
industrial
and commercial operations (i.e. grease trap waste: GTW).
More precisely, the process for producing unsaturated and saturated free
fatty acids, according to the present invention is characterized in that it
comprises
the steps of:
a) selecting a starting material from the group consisting of trap oils, trap
greases, brown greases, and grease trap waste;
b) pretreating the oils and/or greases selected in step a) in order to
separate the oils and/or greases from water and obtain a mixture of
saturated, unsaturated free fatty acids and impurities;
c) subjecting the mixture obtained in step b) to a first purification step by
fractionating the mixture obtained in step b) in three fractions: a light
fraction principally constituted of volatile compounds and water, an
intermediate fraction mainly constituted of free fatty acids, and a
residual heavy fraction mainly constituted of poly-glycerides and
polymers;
d) fractionating the free fatty acids fraction in two fractions: saturated
fatty
acids (SFA) and unsaturated fatty acids (UFA); and
CA 02466834 2010-02-01
e) subjecting the saturated fatty acids and unsaturated fatty acids to a
second purification step in order to obtain oleic acid and stearic acid
and their respective unsaturated and saturated fatty acid residues.
The present invention is also concerned with the use of trap oils, trap
greases, brown greases, and/or grease trap waste for the production of
biodiesel,
solvents and additives for diesel fuel.
The present invention will be better understood upon reading the following
non-restrictive detailed description.
DETAILED DESCRIPTION OF THE INVENTION
In the process according to the present invention, residual oils, fats and
greases, referred herein as Grease Trap Waste (GTW) constitute the starting
material to be treated. The GTW derives from post-consumers and/or by-
products of industrial and commercial. operations.
Compared to yellow greases (YG) which are recuperated in special
containers inside restaurants and food industries (i.e. no other contact with
water
than that of the food moisture), grease trap waste (GTW) are generally
collected
in the traps installed on the sewage water outlet of restaurants and food
industries. These traps allow the collection of the oils and greases carried
over
with the wastewater of washing operations, before they reach the municipal
sewage network. In the traps, the greases are normally subjected to a natural
enzymatic hydrolysis. The glycerin is then washed by the wastewater liberating
most of the free fatty acids of the original triglycerides. As a result of the
different
feedstock and washing operations, their composition could be very different,
but
in a good approximation, they are mainly constituted of a mixture of floating
oils
11
CA 02466834 2004-04-28
WO 03/038020 PCT/CA02/01684
and greases (5 -10%), water (90 - 95%) and residual solids (1 to 3%) (see
Figure
NO 1).
At room temperature, grease trap waste (GTW) forms a non-
homogeneous unstable emulsion. They have a strong odor characteristic of
acetic and/or butyric fermentation (i.e. fermentation of olives before oil
extraction). The grease trap waste (GTW) may be pretreated by decantation,
filtration and centrifugation. Canadian patent applications No. 2,307,450
filed on
May 2, 2000 and No. 2,310,992 filed on June 8, 2000 described methods for
suitably pre-treating GTW according to the present invention.
Pretreatment of residual oils, fats and greases is a very important step to
obtain a lipidic starting material that can be esterified into methyl esters
and used
as biodiesel. Moreover, the present application describes methods that could
be
used for the methyl esterification of different fractionated products (i.e.
FOG,
FFA, residue UFA, Oleic acid, residue SFA, Stearin and Purified Stearin: see
figure 2). Examples for FOG, FFA and SFA are shown.
Generally, the first step in the treatment of GTW is a primary room
temperature decantation in which grease trap waste (GTW) are separated in
three layers (floating, liquid and sludge). A typical example of a mass
balance
following this operation is as below:
Input Output
Top: Floating 8%V
GTW 100 % Middle: Liquid 58 % V
12
CA 02466834 2004-04-28
WO 03/038020 PCT/CA02/01684
Bottom: Sludge 34 % V
The bottom layer (34%), generally named "sludge layer", is mainly
constituted of water and solids, and it is subsequently separated in two
phases
by centrifugation. By this operation, a water phase (2/3 V) can be removed
from a
residual concentrated sludge (1/3 V) (see Figure N 1).
The middle layer (58 %V) as well as the water phase coming from the
sludge layer separation (2/3 V) are then treated in a Dissolved Air Flotation
unit
before being disposed in the municipal sewage network (see Figure 1).
The top layer (8%), named "floating layer", is hot filtered at about 60 C to
about 95 C in order to eliminate any suspended solids. This operation may be
carried out with a rotary screen filter set up to remove particles greater
than 500
m. After filtration, a three-phase centrifugation is performed and generally
give
the following material balance:
Input Output
Top: FOG 35 %V
Floating 100 %V Middle: RAG 35 %V
Bottom: Sludge 30 %V
The middle layer (RAG: oil, water & solids) and the bottom layer (Sludge:
solids & water) are disposed under strict municipal requirements (see Figure N
1).
13
CA 02466834 2004-04-28
WO 03/038020 PCT/CA02/01684
The top layer, named FOG, is essentially free of water and it is constituted
of a mixture of free fatty acids, tri, di, and monoglycerides, trimer & dimer
acids,
oxidized monomers (light fraction), unsaponifiables and other colored long
chain
oxidized products. A typical composition of FOG is presented in Table 1.
Once the FOG has been obtained it can be used as such for the
preparation of esters (i.e. FOG methyl ester) or it can be further
fractionated.
See figure 2 for different fractions and yields.
A first purification step or deodorizing step is intended to remove: lights
fraction (i.e. volatile compounds responsible for strong odor) & water (if
any) and
heavy fraction (i.e. colored material principally composed of poly-glycerides,
polymers and their products of oxidative decomposition). This separation can
be
performed with different distillation techniques (i.e. falling film
evaporation, wiped
film evaporation, fractional distillation and molecular distillation).
One particular option is a deodorization which consists of steam stripping
followed by a distillation which is carried out at a temperature ranging from
150
to 200 C and at a pressure varying from 2 to 3 mbar (Deo-distillation) of FOG.
As
shown hereinafter in Example 2, we described the conditions used for this
first
purification. Typical composition of free fatty acids (FFA) obtained is
described in
Table N 1.
Further fractionation can be done to split the free fatty acids fraction (FFA)
in free unsaturated (UFA) and free saturated (SFA) fatty acids. Suitable
fractionation methods includes:
14
CA 02466834 2004-04-28
WO 03/038020 PCT/CA02/01684
a) By quenching free fatty acids fraction (FFA) oil in a solvent at low
temperatures. Solvent may be selected from the group consisting of hexane,
acetone, isopropyl alcohol and ethanol. Temperature range is about -5 C to
about -20 C. Unsaturated fatty acids (UFA) are dissolved in the solvent while
saturated fatty acids (SFA) precipitate under these conditions. Filtration can
be easily performed in a filter press, a Sparkler filter, a centrifuge or
similar
equipment.
b) By crystallization of saturated fatty acids (SFA), present in the free
fatty acids
fraction (FFA), using a detergent that coats the crystals, then increasing
their
specific weight.
c) By dry fractionation, based on the differences between the melting points
of
saturated (SFA) and unsaturated (UFA) free fatty acids. The principal
advantages of this technology are that there is no solvent requirement and
temperature range is higher than in previous cases (i.e. over zero degrees).
Crystallization is normally carried out by a detailed program of cooling (i.e.
precision of 0.10C). It is important to note that unsaturated fatty acids
(UFA)
and saturated fatty acids (SFA) are mutual contaminants. Poor filtration lets
important quantities of UFA in SFA reducing the yield of UFA and decreasing
the purity of SFA. This problem can be successfully overcome by using a
filter press under pressure. Pressure is generated by squeezing the
membrane, which wraps the filter cloth. A refrigerated liquid or gas can
generate the pressure in order to keep the right temperature of
crystallization.
Pressures can vary from 10 bars to 30 bars.
Typical composition of unsaturated free fatty acids (UFA) and saturated
free fatty acids (SFA) obtained under dry fractionation are presented in Table
NO
1. As shown, the unsaturated fatty acid fraction (UFA), is composed of about
CA 02466834 2004-04-28
WO 03/038020 PCT/CA02/01684
87.7% of oleic acid, linoleic acid and linolenic acids whereas the saturated
fatty
acids (SFA) fraction, is composed of 65.9% of saturated fatty acids. The UFA
and
the SFA fractions obtained from GTW thus have a very interesting commercial
value.
A second purification step is intended to get reduced color and odor in the
respective fractions. This separation can also be performed with different
distillation techniques (i.e. falling film evaporation, wiped film
evaporation,
fractional distillation and molecular distillation). In a preferred
embodiment, this
purification step may be carried out by combining a deodorization step which
consists of steam stripping followed by a distillation step carried out at a
temperature varying from 1500 to 200 C and at a pressure varying from 2 to 3
mbar (Deo-distillation). As shown hereinafter in Example 4, we described the
conditions used for this second purification.
Typical composition of oleic acid and stearin obtained is described in
Table NO 1. Total unsaturated fatty acids raised to 91.7% in Oleic acid
fraction
and total saturated fatty acids in Stearin fraction (62.5%) remain close to
the
values of SFA (65.9%).
Hydrogenation of saturated fatty acids (SFA) results in the production of
purified stearin mainly constituted by palmitic (45%) and stearic (51 %)
acids. As
shown in Example 6, the hydrogenation conditions are described. Typical
composition of the hydrogenated stearin is described in Table NO 1.
Methyl esterification of different products of fractionation: floating oils
and
greases (FOG), free fatty acids (FFA) and saturated fatty acids (SFA) are
16
CA 02466834 2004-04-28
WO 03/038020 PCT/CA02/01684
described in Examples 7, 8, and 9. Characterization of the products obtained
is
presented in Table NO 2.
The following examples are illustrative of the wide range of applicability of
the
present invention and are not intended to limit its scope. Modifications and
variations can be made therein without departing from the spirit and scope of
the
invention. Although any methods and materials similar or equivalent to those
described herein can be used in the practice for testing of the present
invention,
the preferred methods and materials are described.
EXAMPLE 1: Pretreatment of GTW.
10 metric tons of Grease Trap Waste (GTW) coming from the food
industry of the Boston metropolitan area was decanted in tank at room
temperature for 48 h. The upper floating layer (800 L) was separated and
heated
to 90 C until a very fluid solution was obtained. This solution was hot
filtered in a
UNI-FRAMETM rotary screen to eliminate particles greater than 500 m. The
filtered solution was centrifuged in a 3-phase centrifuge to obtain 280 L of a
floating oil and greases (FOG) fraction. Composition of FOG is presented in
Table NO 1.
EXAMPLE 2: First purification (Deo-Distillation) of FOG.
10 Kg of FOG are deodorized and distilled following the process
conditions described herein:
St Temperature Pressure Time (min) Steam
17
CA 02466834 2004-04-28
WO 03/038020 PCT/CA02/01684
Purification (C) (mbar) injection (%)
Deodorization 150 2 60 1,5
Distillation 200 3 30 0,5
At the end of deodorization the product is not cooled but immediately
distilled.
Yields for each fraction (i.e. lights, FFA and heavies) are shown in figure 2.
Characterization of FFA is presented in Table NO 1.
EXAMPLE 3: Dry Fractionation of FFA.
Free fatty acids (FFA) are heated to 60 C until complete dissolution. A
detailed program of nine cooling steps follows. The crystallization conditions
were:
Cooling Tem erature (C) Step Time Cooling Speed Cumulative Time
Step Initial Final OT (min) (C / min) (min)
1 60 60 0 60 0 60
2 60 40 20 20 1 80
3 40 40 0 40 0 120
4 40 20 20 40 0,5 160
5 20 20 0 20 0 180
6 20 10 10 40 0,25 220
7 10 10 0 80 0 300
8 10 5 5 10 0,5 310
9 5 5 0 65 0 375
The filter is pre-cooled to the same temperature of filtration (i.e. 5 C) and
this temperature maintained all over the filtration time. Yields for each
fraction,
Unsaturated Fatty Acids (UFA) and Saturated Fatty Acids (SFA), are shown in
figure 2. Characterization of them is presented in Table NO 1.
18
CA 02466834 2004-04-28
WO 03/038020 PCT/CA02/01684
EXAMPLE 4: Second purification (Deo-Distillation 2a) of UFA.
Unsaturated fatty acids coming from the dry fractionation are deodorized
and distilled following the process conditions described herein-
2" Temperature (C) Pressure (mbar) Time (min) Steam
Purification injection (%)
Deodorization 150 3 60 2
Distillation 200 3 45 0,5
At the end of deodorization the product is not cooled but immediately
distilled. Yields for each fraction, Oleic acid and residue UFA, are shown in
figure
2. Characterization of Oleic acid fraction is presented in Table NO 1.
EXAMPLE 5: Second purification (Deo-Distillation 2b) of SFA.
Saturated fatty acids coming from the dry fractionation are deodorized and
distilled following the process conditions described herein:
2" Temperature (C) Pressure (mbar) Time (min) Steam
Purification injection (%)
Deodorization 150 3 60 2
Distillation 200 3 45 0,5
At the end of deodorization the product is not cooled but immediately
distilled. Yields for each fraction, Stearin and residue SFA, are shown in
figure 2.
Characterization of Oleic acid fraction is presented in Table NO 1.
19
CA 02466834 2004-04-28
WO 03/038020 PCT/CA02/01684
EXAMPLE 6: Hydrogenation of Saturated fatty acids (SFA) fraction.
The saturated fatty acids (SFA) fraction obtained after dry fractionation is
hydrogenated in a Parr reactor at 20 bar of hydrogen pressure during 2 hours
at
205 C. The catalyst (22% Nickel) was used at 0.2 % (W/W SFA basis). After
hydrogenation, the catalyst was filtered and the product obtained was deo-
distilled in the same way of the second purification previously described.
Characterization of Purified stearin is presented in Table NO 1.
EXAMPLE 7: Esterification of FOG
5 Kg of a FOG (acid value = 168 mg KOH / g) were reacted with 3374 g of
methanol at reflux temperature in presence of 75 g of an acidic catalyst.
After a
hour reaction, two phases were clearly observed. The bottom one
corresponds to methyl esters and the top one to methanol. Three washings with
hot water (2.5L each) were performed over 1 minute with very slow stirring of
the
ester phase. Anhydrous Na2SO4 (25 %w) was added to the organic phase to
20 remove residual water. After drying (30 min) the acid number was 3.3 mg KOH
/
g. In order to further reduce the acid number, A1203 (20%w) was added and the
temperature increased to 140 C. After 20 minutes, filtration was performed
and
the acid number was reduced to 0.4 mg KOH / g. The yield for esterification
reaction is more than 75% and the full characterization of the product
obtained is
presented in Table NO 2.
EXAMPLE 8: Esterification of free fatty acids fraction (FFA).
5 Kg of a free fatty acids fraction (FFA) with an acid number of 181 mg
KOH / g were reacted with 3374 g of methanol at reflux temperature in presence
of 75 g of an acidic catalyst. After a 20-hour reaction, two phases were
clearly
CA 02466834 2004-04-28
WO 03/038020 PCT/CA02/01684
observed. The bottom one corresponds to methyl esters and the top one to
methanol. Three washings with hot water (2.5L each) were performed over 1
minute with very slow stirring of the ester phase. Anhydrous Na2SO4 (25 %w)
was added to the organic phase to remove residual water. After drying (30 min)
the acid number was 3.5 mg KOH / g. In order to further reduce the acid
number,
A1203 (20%w) was added and the temperature increased to 140 C. After 20
minutes, filtration was performed and the acid number was reduced to 0.5 mg
KOH / g. The yield for esterification reaction was more than 80% and the full
characterization of the product obtained is presented in Table NO 2.
EXAMPLE 9: Esterification of the Saturated Fatty Acid (SFA) fraction.
A saturated fatty acid (SFA) fraction was esterified using substantially the
same procedure described in Examples 7 and 8. The yield for esterification
reaction was more than 80% and the full characterization of the product
obtained
is presented in Table NO 2.
The fractions used as examples for esterification (FOG, FFA, and SFA)
don't limit the use of the others fractions (UFA, Residue UFA, Oleic Acid,
Residue SFA, Stearin or Purified stearin) that could also be obtained by using
the
same method of the present invention.
Esterification was performed with an excess of the stoechiometric quantity
of methanol. The reaction was carried-out at reflux temperature in presence of
an
acidic catalyst (i.e. HCI, H2SO4, H3PO4, p-toluenesulfonic acids or some
acidic
resins) during a period varying between 10 h to 40 h, more preferable between
10 h and 20 h.
Different analysis were performed on the products obtained by external
laboratories specialized in diesel fuels. The results are summarized in Table
NO
2.
21
CA 02466834 2004-04-28
WO 03/038020 PCT/CA02/01684
Distillation (ASTM D86): The distillation range is used to determine the
calculated cetane index.
Cetane Calculated Index (ASTM D976): It is based on specific gravity and
the 10, 50 and 90% distillation temperatures to give numbers that correlate
with
the cetane engine test method.
Cloud Point (ASTM D2500): Is the temperature at which a cloud of crystals
first appears in a liquid when cooled under determined conditions. Three
cooling
baths (Ti = -1 C to - 3 C; T2 = -15 C to - 18 C and T3 = -30 C to - 40 C were
used. Thermometer was completely immersed into the sample.
Pour Point (ASTM D97): Is an index of the lowest temperature at which it
has utility in certain applications. Only the bulb of the thermometer was
immersed
into the sample.
From the results obtained, it is clear that the present invention provides a
new and useful industrial application of residual oils, fats and greases.
Indeed,
unsaturated fatty acids and saturated fatty acids of commercial value were
obtained from GTW. Furthermore, characterization of the methyl esters obtained
satisfy the requirements of the U.S. National Biodiesel Board (NBB) and are
very
closed to those of commercial products (i.e. GRIFFIN BIO G300TM) confirming
the potentiality of the various fractions obtained as biofuels.
While several embodiments of the invention have been described, it will be
understood that the present invention is capable of further modifications, and
this
application is intended to cover any variations, uses, or adaptations of the
invention, following in general the principles of the invention and including
such
departures from the present disclosure as to come within knowledge or
customary practice in the art to which the invention pertains, and as may be
22
CA 02466834 2004-04-28
WO 03/038020 PCT/CA02/01684
applied to the essential features hereinbefore set forth and falling within
the
scope of the invention.
23
CA 02466834 2004-04-28
WO 03/038020 PCT/CA02/01684
a ~ o e p O e Q N o
~ c b !a p
N O ~ O ~p O O
t p ~ O
91
N w N w c a - cy ~, a v, o --ti $
O m {V
3
o
m c~ co m o N tf v we v v o of r d a s .f
94
O
44
0
,b9
N L C o g r o o o u 0 0 o r o 0 ~ ,~ o o$ h o
~.J a m e- n cY iY m .- o H o d m t7 ti ~4 ~n
C a Cr m m o d d o== of d v d d tai == to c =n
4-I
45 C3 ~aH}l
Q p
w C3
aa s o .- ti o ,e m N cJ ~v t"
R~ r ~, n~ o I+l a ui y m o m y n~ n
f~ pp p p 1~
V G Y7 F O S -O.. ' O d O ' Oq, Q1 M It
4-J V 8Q t Oy r w ovci
U ~ ~ t4 ~ N r ~ O O b ~ N r 0 ~
O O O O O O v N
O F
T m co IV 0
O
o gN .~~~ 8
93
in c:
ro 24
H
CA 02466834 2004-04-28
WO 03/038020 PCT/CA02/01684
O OP=N t~a0p~y'~rMpQO to r^C~7tU ~7p
C~GlO C',r*'0~ O~ NcgrSM G~..O
d to O ct t0 (p '~ Q h tq Ln O LA O p N 0 cV
cd(DLnO - rN O
U. ot~LriM(O Lao NN- ro 04 mcN*)rMim"-
p~pN a 0co LgUl L~LfjGOptn Ln
NL.. N00 oio0~--pm0 (Otf)u~~b00~*' C]
N
~ p~T*"OO O~ Cp7~t'J
MC7~Q~
ooD Nm co OapM LO
5-5 0
O C'3 133 - O C c
O
cn c'~ EE E E EE t= E Om O Otaq ENO Ln Npa
C
L. p C? co O v O (7 N
.J *' 4 D w 0 0 CS O G c
$ O eh tG et `~t
F-~~~~~o F ~~ CU'.)CU'7
¾d~N¾
d Q a ~r¾a d's d a¾
$ Y
....,
V X N UUU
LO e p 5 vyv Q1
0
=p ..O O O O_ N
a $UU td U EU~3 a'.~' ~~. of 4)
o c= o
oa .0 P, =
`LSc cpc v c E i c o caQ~v~i~tj a a._'yG ~. z c -5 R
a ooo o~ c
.. r4 Lgi a E
Lei a~ H m 4~ .. LO CO
o c
U{ o m ~L CAS
CL OIQ
