PROCEDE POUR L'OBTENTION D'HUILES ALIMENTAIRES RAFFINEES ET DE PRODUITS DESTINES A L'INDUSTRIE DES ALIMENTS POUR ANIMAUX A PARTIR D'HUILES VEGETALES OU ANIMALES BRUTES ET DE SILICES ABSORBANTES

PROCESS FOR THE PRODUCTION OF REFINED EDIBLE OILS AND PRODUCTS FOR FEEDSTUFF ANIMAL INDUSTRY FROM VEGETABLE OR ANIMAL RAW OILS AND ABSORBENT SILICAS

Abrégé anglais

There are numerous processes to refine vegetable or animal oils. All
of these processes give by-products with little or no value and pollutant
effluents.
In this invention we have found that these disadvantages can be
overcome by treating directly the raw oil with absorbent silicas produced
particularly by precipitation of alkali silicates with acids.
The oil is then separated from the silica saturated with the molecules
other than triglycerides. The saturated silica which holds back a small amount
of oil becomes a good product for feedstuff animal industry with a good
energetic value.
No wastes nor effluents occur in the process.

Revendications

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The embodiments of the invention in which an exclusive property or
privilege is claimed are defined as follows:
1. A process for treating raw vegetable oil and raw animal oil which
comprises the use of absorbent silica and allows to obtain a refined
vegetable oil or a refined animal oil and a product for feedstuff animal
industry, compounded more particularly with the absorbent silica, the
molecules retained on silica and a small quantity of triglycerides.
2. A process as defined in claim 1 in which the oil is of vegetable origin.
3. A process as defined in claim 1 in which the oil is of animal origin.
4. A process as defined in claim 1, 2 or 3 in which the absorbent silica
used is a precipitated silica usable in feedstuff animal industry.
5. A process as defined in claim 1, 2 or 4 in which the oil is a fruit oil
(palm, olive,...) or a seed oil (soya, rapeseed, sunflower,...).
6. A process as defined in claim 1, 3 or 4 in which the oil is a mammals
oil (whale, seal,...) or a fish oil (salmon, herring, cod,...).
7. A process as defined in claim 1,2,3,4,5 or 6 in which the precipitated
silica has an average agglomerate size between 50 and 120 µm.

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8. A process as defined in claim 1,2,3,4,5,6 or 7 in which the
precipitated silica has an average surface area between 50 and 250
m2/g.
9. A process as defined in claim 1,2,3,4,5,6,7 or 8 in which the oil is
percolated through a silica bed placed in a column. The progressive
saturation of the silica is obtained when the white silica changes to a
brownish colour.
10. A process as defined in claim 1,2,3,4,5,6,7,8 or 9 in which the
percolation is realized at room temperature (20°C.)
11. A refined oil as defined in claim 1,2,3,4,5,6,7,8,9 or 10.
12. A product for feedstuff animal industry as defined in claim
1,2,3,4,5,6,7,8,9,10 or 11.

Description

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SPECIFICATION
This invention relates to a process for the production of refined edible
oils and products for feedstuff animal industry from vegetable or animal raw
oils and absorbent silicas.
This is understood in what comes after for raw vegetable oil as a
mixture of molecules extracted from oily plants or fatty parts of animals by
mechanical means (pressing, crushing ...), physical and chemical means
(stripping, hexane extraction,...).
This mixture generally consists of triglycerides (90 to 99% in weight)
formed in living organisms by esterification of three hydroxyles functions
with
fatty acids (organic acid with long hydrocarbon chain which can include one
or several double bonds).
The other compounds (1 to 9%) which are present in raw vegetable and
animal oils are generally free fatty acids, mono and diglycerides formed by
esterfication of one or two hydroxyles functions of glycerol with an organic
acid, phosphoglycerides which contain at least one atom of phosphorous,
molecules coming from secondary metabolisms like steroids, tocopherols,
carotenes and sugars.
The molecules which do not contain fatty acids are non-saponifiable as
they cannot be transformed in soap.
These molecules must be removed to allow the refining oil to be of good
standard for human use.
The food quality can be obtained with several technologies.
The processes used are of chemical or physical type or a combination
of the two.

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The chemical processes use slightly acidic aqueous solutions which are
put in contact with oil in a first stage to extract in the aqueous phase,
among
others, phosphoglycerides and polar molecules. The oil phase is further
treated with an aqueous akali solution to remove essentially free fatty acids.
The oil is then filtered using clays or more uncommonly using silicas to
make the finishing treatment before marketing. (P.J. Wan, American Oil
Chemist Society, Introduction to Fats and Oil Technology 1991, pages 85 -
131 and pages 137 - 163).
The physical refining processes allow the elimination of the major part
of molecules other than triglycerides.
A finishing treatment, as stated before, on clays or uncommonly on
silicas can be done to give an edible oil.
In any case, the silica is used only in finishing treatment after a chemical
and/or physical treatment of the raw oil. (K. Carlson, Inform, American Oil
Chemist Society, Vol. 4, no. 3, pages 272 - 275, 1993).
The industrial refining technologies generate at each stage by-products
and wastes of little or no value which carry away a small quantity of
triglycerides which gives rise to a weight loss (5% - 10%) between the raw oil
and the refined oil.
We have found that these disadvantages may be overcome by treating
directly raw vegetable oil and raw animal oil with absorbent silicas.
The oil is then separated from the silica saturated with the molecules
other than glycerides. The saturated silica which holds back a small quantity
of oil becomes a good product for feedstuff animal industry with a good
energetic value. (Figure 1 )

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The invention arose from the surprising established facts of science: the
absorbent silicas can trap in raw oil non-saponifiable molecules, mono and
diglycerides, phosphoglycerides, metals in trace without acidic or alkali
washing, stripping with steam or filtration on clays.
The refined oil is generally separated by filtration or percolation. The
filtration can be made up with the saturated silica and can be used without
modification as a product for feedstuff animal industry.
This refining process is water-free; consequently it does not generate
aqueous water polluted effluents. The quantity of silica used is directly
linked
to the quantity of molecules other than triglycerides found in raw oil.
The molecules that are liable to unpleasant taste or smell of oil are
trapped on the absorbent silica.
This technology does not produce any kind of waste. It is a clean
technology well adapted for a small factory which does not request important
investment.
The process of the invention can be implemented with oils from fruits
(palm, olive ...); oils from seeds (soya, rapeseed, sunflower,...) as well as
seal
oil, fish oil etc.
A favorite implementation uses silica with a size of agglomerates
between 50 and 120 ~m and a surface area between 50 and 250 m2/g.
In these conditions, the fixation of molecules other than triglycerides is
very efficient without any disadvantage for the moving of triglycerides around
and inside the silica particles.
Another favourite implementation is to arrange silica in the bottom of a
column and to percolate oil on it under pressure.

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The saturation of the silica is obtained when the white silica turns to
brownish colour.
Depending on the quality of raw oil and of the characteristics of the
silica, 1 kg of silica allows generally to refine 10 to 15 kg of oil.
The saturated silica is then removed from the column and used without
any modification as a product for feedstuff animal industry.
We claimed the quality of new products for the refined oils and the
products for feedstuff animal industry described below.
The invention is illustrated by the following examples:
EXAMPLE NO. 1:
We put in a glass column (1 ) (diameter: 0.04m, height: 0.8m), 0.04 kg
of absorbent silica (2) (average size of agglomerates : 60 Vim, average
surface area : 100 m2/g) retained by a cellulose filter (3) put on a metallic
framework (4) (Figure 1 ).
The soya oil stored in the container (5) has been obtained with an
hexane extraction of soya seeds. The average value of the acidity of the raw
oil expressed in % of weight of oleic acid is of 1.2%.
0.3 kg of raw oil is then placed in the column (1 ) at room temperature
with a device including a pump and a flood gate (7). A pressure of 16 p.s.i.
is applied with a compressor (7) fitted with a flood gate (8) after closing
the
flood gates (6).
The average value of 0.9 I/h is measured for the flow rate.
The saturation of the silica is obtained for an addition of 0.2 kg of soya
raw o i I .

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0.47 kg of refined oil (9) has an acidity expressed in % weight of oleic
acid lower than 0.1 % which allows its use in human feeding.
The saturated silica (10) is removed from the column and directly used
as a product for feedstuff animal industry.
EXAMPLE NO. 2:
We put in a glass column (1 ) (diameter: 0.04m, height: 0.8m) 0.04 kg
of absorbent silica (2) (average size of agglomerate 100 ~.m, average surface
area: 190 m2/g) retained by a cellulose filter (3) put on a metallic framework
(4) (Figure 1 ). The sunflower oil stored in the container (5) was been
obtained
with an hexane extraction of dehulled seeds. The average value of the acidity
of the raw oil expressed in % of weight of oleic acid is 1.1 %.
0.3 kg of raw oil is then place in the column (1 ) at room temperature
with a device including a pump and a flood gate (7). A pressure of 16 p.s.i.
is applied with a compressor (7) fitted with a flood gate (8) after closing
the
flood gate (6). The average value of 1.8 I/h is measured for the flow rate.
The saturation of silica is obtained after another addition of 0.25 kg of
raw sunflower oil.
0.52 kg of refined oil (9) has an acidity expressed in % weight of oleic
acid lower then 0.1 % which allows its use in human feeding.
The saturated silica (10) is removed from the column and directly used
as a product for feedstuff animal industry.
EXAMPLE NO. 3:
We put in a polyvinylchloride (P.V.C.) Column (1 ) (diameter: 0.5 m,
height :0.8 m) fitted with a window in plexiglass (width: 0.04m, height 0.7m),

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kg of absorbent silica (2) (average size of agglomerates: 100 ~,m, average
surface area : 190 m 2/g) retained by a synthetic textile filter (3) put on a
metallic framework (4) (Figure 1 ).
The seal oil stored in the container (5) has been extracted from the
blubbers of harp seals. The average value of the acidity expressed in % of
weight of oleic acid is of 1.4 %.
30 kg. of raw oil is then placed in the column (1 ) at room temperature
with a device including a pump and a flood gate (7).
A pressure of 12 p.s.i. is applied with a compressor (7) fitted with a flood
gate (8) after closing the flood gate (6). The average value of 3.8 I/h is
measured for the flood rate.
The saturation of silica is obtained after another addition of 27 kg of raw
seal oil.
53 kg of refined oil (9) has an acidity expressed in % weight of oleic acid
lower than 0.1 % which allows its use in human feeding.
The saturated silica is removed from the column (10) and directly used
as a product for feedstuff animal industry.
EXAMPLE NO. 4:
We put in a polyvinylchloride (P.V.C.) Column (1) (diameter: 0.5m,
height: 0.8m) fitted with a window of plexiglass (width: 0.04m, height: 0.7m),
5 kg of absorbent silica (2) (average size of agglomerates: 100 ~,m average
surface area: 190 m2/g) retained by a cellulose filter (3) put on a metallic
framework (4) (Figure 1 ).

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The seal oil stored in the container (5) has been extracted from the
blubbers of harp seals. The average value of the acidity expressed in % of
weight of oleic acid is of 0.9%.
35 kg of raw oil are then placed in the column (1 ) at room temperature
with a device including a pump and a flood gate (7).
A pressure of 14 p.s.i. is applied with a compressor (7) fitted with a flood
gate after closing the flood gate (6). The average value of 4.2 I/h is
measured
for the flood rate.
The saturation of the silica is obtained after another addition of 35 kg of
raw seal oil.
67.5 kg of refined oil (9) has an acidity expressed in % weight of oleic
acid lower than 0.1 % which allows its use in human feeding.
The saturated silica (10) is removed from the column and directly used
as a product for feedstuff animal industry.

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