Note: Descriptions are shown in the official language in which they were submitted.
l~.Z~3779
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The invention provides a process for improving the
properties of meals or flours of oily seeds by reducing
their content of lipoid and water soluble compounds which
have a negative influence on their smell, taste, nutrî-
tive value and physiological acceptability. The smell is
~ adversely affected for example by secondary products of
oxidation reactions of unsaturated fatty acids; peptidss
containing certain components cause a bitter taste; some
glycosldes such as mustard oil glycoside are toxic; and
nucleic acids can provoke a pathological condition suchas gout or urinary calculi. Application of flours of oily
seeds in fodder and especially food is thus limited to a
large extent by the content of such compounds.
It is therefore the object of the present invention
to remove lipoid compounds such as fat oxidation produots,
nucleic acids, peptldes containing large amounts of hydro-
phobic amino acids, and glycosides from ground oily seeds,
and thus to increase the protein amount which is deci~sive
for the nutritive value.
According to known processes, the lipides are removed
,
from cells by organic solvents, and the content of ama- -
roids and toxic metabolites is reduced by extraction with
water. However, the long extraction time is disadvantage- ~
ous, and the treatment of flours of oily seeds with orga- -
nic solvents such as hexane is time-consuming as well and
yields products which, because of their content of resi-
dual fat (l to 4 ~) are neither free from disagreable
smell nor stable in taste.
29 In accordance with this invention, there has been
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found a process for improving the properties of meals or
; flours of oily seeds by reducing their content of lipoid
and water-soluble compounds, which comprises treating the
crushed or ground seeds with a liquid extractant compris-
ing ammonia or ammonium hydroxide and an organic solvent
of the formula I
R1 - (CnH2n) ~ OR2 (I)
in which either
R1 and R2 each are hydrogen and n is 1, 2 or 3; or
R1 is a hydroxy group, R2 is hydrogen, methyl or ethyl,
and n is 2 or 3;
and after having removed the liquid extractant, washing
the residue of the seeds with water.
As crushed or ground seeds there are used oily seeds
the meals or flours of which, after degreasing, are con-
sidered as protein carriers, for example soybean, rape,
peanut, sunflower or cotton seeds.
Suitable solvents of formula I are advantageously al-
cohols such as methanol, ethanol, n-propanol or isopropa-
nol. Preferred are methanol and ethanol, especially metha-
nol. Apart from the citad alcohols, glycols and their
;~ monoethers of formula I may be employed, especially glycol
or monomethylglycol.
Ammonia can be added to the cited solvents either~in
gaseous form (NH3) or as concentrated aqueous solution
(NH40H), depending on the water content of the meal or - -
flour, and on the amount of the solvent used and the water
content thereof. NH40E~ is suitable ~or flour having a low
29 moisture content (O to 15 % ), NH3 is appropriate in the
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case of cell masses containing more water (10 to 30 %)~
Removal of the lipoid compounds depends on the total
- water content (in weight % relative to the amount of sol-
vent used) and on the NH3 concentration (in weight %, re-
lative to the solvent used).
Especially good results are obtained at a meal or
flour/solvent weight ratio of from 1:3 to 1:10 when r,letha-
nol or ethanol is used, and f`rom 1:8 to 1:15 in the case
of employing propanol, glycol or monoglycol ethers. The
corresponding ammonia concentration, relative to the amount
of solvent, is from 1 to 15, preferably 5 to 10, weight %.
The sum of the water amounts present in the cell mass, sol-
vent and, optionally, aqueous ammonia, is from O to 30,
preferably O to 20, especially O to 10, weight ~, relative
to the solvent amount used.
'rhe fats are separated from the crushed or ground
seeds by suspending the flour in the solvent, and NH3 is
introduced or NH~OH is added subsequently. The suspension
is advantageously agitated in order to ensure thorough in- ~ -
: .
termixing. The temperatures of the treatment are general-
ly in a range of from -2 to +60C, preferably 5 to 50C,
and especially 10 to 30C. The time of treatment is from
5 to 180? preferably 35 to 60, minutes. Generally, the
treatment is carried out under normal pressure.
After the solvent/ammonia treatment is completej the ;
degreased residue is separated from the solvent according
to any usual method such as centrifugation, filtration or
sedimentation; filtration ~eing preferred.
29 In order to remove the lipids as completely as pos-
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sible, the solid residue obtained can be treated again with
an organic solvent. For removing solvent remainders and
ammonia, the residue can be dried, advantageously under
reduced pressure, preferably of from 80 to 150 ~m Hg, and
at slightly elevated temperatures, preferably of-from 40
to 50C. The products so degreased and dried are odorless
and nearly white.
The liquid phase separated frorn the solid phase ac-
cording to the above method contains ammonia and lipoid
compounds. The solvent used can be separated from the fats
by vacuum distillation, and reused. The remaining fats
can be subsequently subjected to the usual fat refining
- operations.
Subsequently, the degreased and optionally dried
flours are absorbed in water. Preferred are such amounts
of water which are in a weight ratio of from 1:t to 1:30,
especially l:5 to 1:i5, to the meal or flour; at least,
the quantity of water must allow agitation of the suspen-
sion.
During the treatment with water, the pH should be in
the range of from 4 to ~.5, preferably 5 to 7.5. Optional-
ly, it has to be adjusted correspondingly, which is re~uir-
ed above all in the case where flours from the first extrac-
tion steps are used which are not at all or incompletely
dried and thus contain residual amounts of ammonia possib-
ly causing a high pH. This extraction is to reduce the
content of undesirable metabolites such as nucleic acids,
bitter peptides or toxic glycosides, and it is generally
29 carried out at a temperature of from 30 to 95C, preferably
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40 to 70C, especially 50 to 60C, under normal pressure.
Depending on the extraction temperature and the amount of
water, the extraction time is in a range of from 5 to 120 ~-
minutes; good results are obtained within a period of
from 25 to 45 minutes. For separating solid and liquid
components, the suspension is filtered, preferably at
temperatures of from 10 to 30C. Further suitable separa-
tion processes are sedimentation or centrifugation.
The solid phase is liberated from liquid remainders
according to usual methods such as vaccum freeze drying,
vacuum drying or spray drying.
The products have agreable taste and odor, a very pro-
nounced water-binding power, and a white color. These pro- ;
pertiés are not deteriorated even after a several month's
storage.
The products treated according to this invention have
an especially low content of lipoid compounds (0.3 to 0.8
weight %) and nucleic acid (0.4 to O.g weight %), which
makes them particularly appropriate as fodder and additive
for foodstuffs.
The process of the invention avoids the disadvantages
of known solvent extractions such as large solvent amounts
and long treatment times.
The ammonia used in accordance with the invention
does not only act as solvent, but changes also the mecha-
; nical structure of the flours, so that the extraction time
is reduced and the efficiency of the extraction is in-
creased.
29 The following Examples illustrate the invention.
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E X A M P L E 1:
1iO g of ground soybean seeds having a residual moi-
sture of 11 %, 23 % of crude fat (after acidic hydrolysis),
44.6 p of crude protein (N2 x 6.25), 4.3 % of nucleic acids
and 4.8 % of ashes were suspended in 500 g of methanol.
While agitating the suspension, 15 g of NH3 gas were
introduced and dissolved. The temperature was maintained
by cooling at 25 - 35C during this introduction. The mix-
ture of methanol, ammonia and flour was agitat~d for 30 mi-
nutes at 20C.
In order to separate the solid and the liquid phase,the batch was filtered, and the solid residue was extract-
ed once with 100 ml of methanol and once with 300 ml of
acetone. After another filtration, the ~iltrates were
united. This brown solution contained the lipoid com-
pounds of the starting substance. Methanol, acetone and
ammonia were removed by vacuum distillation (100 mm Hg,
40C~. The residue, that is 22.5 weight % of the dry
matter used, was in the form of a brown oil.
The solid residue of the extracted flour obtained in
the filtration was dried for 5 hours in vacuo (100 mm Hg)
at 40C. 80 g of degreased flour having a residual
moisture of 3 % were obtained, which flour was odorless
and had a lighter color than the startlng substance.
In order to reduce the content of undesirable water-~
soluble compounds, this cell mass was suspended in 80o ml
of water. The pH of the suspension homogenized by agita-
tion was 6;9.
29 After raising the temperature to 55C, agitation was
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continued fc,r a further 20 minutes, the batch was cooled to
30C and separated by filtration to give a solid and a li~
quid phase. The sediment obtained was again mixed with
300 ml of water and agitated for 10 minutes at 20C, sub-
sequently filtered again, and finally, the sedimènt wasdried under reduced pressure. Thus, 50 g of a white, odor-
less flour were obtained, which has an agreable srnell in
moist state.
The result of this and the further Examples are list-
ed in Table I.E X A M P L E 2:
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Starting material was the same soybean flour as des-
cribed in Example 1, and it was subjected to the same pro-
cess steps and conditions with the exception that instead
of gaseous NH3 40 ml of concentrated NH40H (33 ~ strength)
were used as reagent.
E X A M P L E 3: ;;
Operations were as in Example 2; however, 30 g of NH3
were used.
E X A M P L E 4:
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Operations were as in Example 2; however, instead of
methanol, ethanol was used as solvent.
E X A M P L E 5:
Operations were as in Example 2. Instead of metha
nol, i-propanol was used as solvent.
E X A M P L E 6:
The soybean flour as described in Example 1 was used
as starting material. 110 g of this flour were extracted
29 as described in Example 3; however, the residue was not
1~ 779
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completely dried. The filter cake remainin~ after a tho-
rough suction-filtration which contained 65 ~ of solid~s
was suspended in 900 ml of water. The pH adjusted itself to
8.5~ because of the ammonla remaining in the moist matter.
The temperature of the suspension was raised to 65C
with agitation, and after 5 minutes, the pH was adjusted
to 6.8 by adding HCl. Subsequently, agitation was cor-
` tinued for a further 15 minutes at 65C, the batch was
cooled to 40C and filtered. The sediment obtained was
dried.
- E X A M P L E 7:
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110 g of rape seeds containing 13 % of water, 42.9 %
of crude fat, 24.7 % of crude protein, 3.7 % of nucleic
acid and 4.6 % of ashes were suspended in 500 ml of metha-
t5 nol, and 50 g of-NH3 were introduced with agitation and at
a temperature of 20C. Subsequently, agitation was con-
tinued for 1.5 hours at the latter temperature, and the
batch was filtered.
The residue was washed twice with each 100 ml of metha-
~ ~ 20 nol and then once with 300 ml of acetone.
;;; At 200 mm Hg and 40C, the residue was dried for 2
hours, and subsequently suspended in 600 ml of water, while~
,"
because of remaining amounts of ammonia a pH of 8.2 adjust~
ed itself. After having raised the temperature to 50C,
25 the pH was readjusted to 6.5 by means of hydrochloric acid,
and the mixture was agitated for 45 minutes at 50C.
After cooling to 30C, the batch was filterecl, where- ~ -
.
after the residue was washed once with 300 ml of` water at
29 20C. Subsequent lyophilization gava 40 g of a light,
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odorless powder.
E X A M P L E &:
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The same rape seed flour as described in Example 7
was used as starting material, which was subjected to the
same process steps and conditions as indicated in Example
7; however, instead of methanol n-propanol ~ras used.
T A B L E
. Some analytic data of the products before and after
the process.
Weight % relative to dry matter.
- Final products
110 g seeds used (ground) (4 % residual mois~ure)
.
Ex. Species Water Crude Nucleic Protein Amount Crude Nucleic Protein
content fat acid fat acid
wt.-% wt.-% wt.-% wt.-% (g) wt.-% wt.-% ~..-%
?soybean 11 23 1~.3 4051.0 0.7 0.6 60.2
2 " 11 23 4.3 I~o 52.3 0.8 0.8 5~.4
3 tl 11 23 4.3 40 49.4 0.4 0.5 63.2
1~ " 11 23 4.3 40 52.8 0.7 0.7 59.1
" 11 23 4.3 40 53.4 0.8 0.~ 58.7
6' . 11 23 4.3 40 49.8 0.5 o.4 62.8
. .
7rape 13 42.9 3.7 20 40.2 ~0.7 0.5 51.2
8 " 13 42~9 3.7 20 42.6 0.8 o.4 49~.5
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