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' 2,413,698
a stares PATENT OFFICE
2,413,698
PROCESS FOR THE RECOVERY OF UNFER;
MENTED AND UNFERMENTABLE SUGARS
FROM SACCHARIFIED
TIONS
STARCH
SOLU- '
Eduard Farber, New-Haven, Conn., and James S. '
Wallerstein, New York, N. Y., assignors to The
Overly Biochemical Research Foundation, Inc.,
New York, N. Y., a corporation of‘ New York
No Drawing. Application July 30, 1943,
Serial No. 496,834
16 Claims. (Cl. 195-38)
-
1
2
or hydroxide is conducted after the fermentation
This invention relates to the separation and
of the sacchari?ed starchy material, ‘the fer
recovery of unfermented and likewise of unfer
merited liquor is preferably ?rst ?ltered to re
mentable sugars from sacchari?ed starch solu
move the yeast which may then be re-used for
tions, and more particularly, to the separation of
fermenting other batches.
maltose and other polyoses from solutions of
We have found that when an alkaline earth"
sacchari?ed starchy materials.
oxide, for example, calcium or strontium oxide,
It is the general object of the invention to
in finely ground form, is added to solutions con
effect efficient removal of maltose and other
taining maltose and other polyoses at relatively
polyoses which either are entirely unfermentable
low temperatures (0° to 40° C.) a precipitate is
or remain unfermented during the particular 10 formed which contains the polyoses in com
conditions of fermentation, for example, alkaline
bination with the alkaline earth oxide. The
fermentation, to which a sacchari?ed starchy
precipitate settles out after a period of standing,
material is subjected.
and may be readily removed from the mother
It is also an object of the invention to provide
liquor by ?ltration, centrifugation, or often by
15
a process for the preliminary purification of sac
simple decantation, preferably at low tempera
chari?ed starchy materials prior to subjecting
tures“. The temperature is not critical within the
such materials to a fermentation during which
specified limits; near the lower limit, formation
the separated sugars are either not converted or
are converted only partially, whereby a fer
of the compound may be slow and filtration dif
?cult; near the upper limit, it is necessary to
merited mash is obtained, in which the content‘ 20 carry out the precipitation quickly, otherwise
of unfermented sugar is greatly reduced over
dark colored decomposition products are formed.
prior procedures, so that the recovery of the con
These occur if the temperature is permitted to
versionproducts, and particularly of glycerol, is
rise substantially beyond the upper limit cited.
greatly facilitated.
The alkaline earth must be thoroughly ad
25
It is a further object of the invention to effect
mixed with the solution for a complete reaction.
I puri?cation of the fermented liquor obtained by
An e?icient way of~carrying this out consists in
the alkaline fermentation of sacchari?ed starchy
treating the mixture in a ball mill or similar
materials, by removal of a large part, if not all,
mechanical mixing device. Subsequently, the
of the unfermented sugar content of the liquor, 30 maltose and other polyoses may be recovered
so as thereby to facilitate and improve the re
from the precipitate by treatment of the com
covery of the products of the fermentation from
’ pound with acids which form insoluble or spar
the liquor.
ingly soluble salts with. the alkaline earth metals,
Other objects and‘ advantages of the invention
the effect here being to convert the alkaline earth
will become clear as the more detailed descrip
oxides into salts and to bring the polyoses into
tion thereof proceeds, and the features of novelty 35 solution. It is particularly advantageous to
will be set forth in the appended claims.
.
In accordance with the present invention, a
sacchari?ed starchy material is subjected, either
form a salt which is but sparingly soluble in order
that the solution of the polyoses may be reason
ably pure for subsequent uses. Thus, for ex
before or after fermentation, to the action of an
ample, maltose may be precipitated with lime
oxide or hydroxide of an alkaline earth metal, 40 and then redissolved by means of sulfuric acid,
and especially of calcium or strontium, whereby
maltose and other polyoses are precipitated in
the form of their more or less insoluble combina
tions with the alkaline earth metal oxide or hy
droxide; whereafter the precipitated material
may be decomposed by means of an acid, prefer
ably one which forms an insoluble or sparingly
soluble compound with the alkaline earth metal,
and the maltose and other polyoses so liberated
forming the sparingly soluble calcium sulfate,
and leaving a fairly pure sugar solution. Gaseous
acid anhydrides which form insoluble or spar
45 ingly soluble alkaline earth metal compounds, are
also effective agents; thus carbon dioxide may be
added down to pH 6.0, the insoluble carbonates
thus formed being readily removed. Sulphur
dioxide may be similarly} employed.
The process is of particular advantage where
may then be acid-hydrolyzed to convert them to 50 the sacchari?ed solution of starchy materials is
glucose or other fermentable sugars. This hy
employed for the production of glycerol by an
drolyzed sugar solution may then be combined
alkaline fermentation. Under these conditions,
With/‘8. new batch of sacchari?ed starchy mate
the glucose is fermented whereas the maltose
rial and subjected to fermentation. Where the
ferments at best very slowly. Any residual un
treatment with the alkaline earth metal oxide 55
2,413,698
3
'
4
fermented sugar (consisting mainly of maltose)
tion with reference to the unfermentable sugars
remaining in the mash will tend to interfere
present. The materials are mixed in a ball mill,
with the subsequent distillation of the glycerol
and the mixture permitted to stand at room tem
from the concentrated slops. Unfermented sugperature of about 25° C. A yellowish brown pre
ars under these conditions tend to form dark 5 cipitate is formed containing disaccharides and
colored and caramel-like compounds which en~
polysaccharides not converted to glucose, in com
trap the glycerol formed by the fermentation and
prevent its ready volatilization by means of
steam. By the use of lime or other alkaline
fermentable under alkaline conditions into in-
bin-ation with the lime. For complete precipita
tion, the solution is cooled to about 5°’ C. over
night. This precipitate is removed by ?ltration.
taken place.
‘
_ ‘
soluble compounds with alkaline earth oxides oi
Meanwhile, the sugar-lime precipitate formed
hydroxides‘
is treated with dilute sulfuric acid the insoluble
The recovered maltose may be used as such or
calcium sulfate formed ?ltered on’, the sugar be_
for alcoholic fermentation under non-alkaline 2n ing thereby redissolved._and the acidity is amidst
a mineral acid like sulfuric, and then fermented
eral hours at temperatures near the boiling point.
to glycerol under alkaline conditions.
the disaccharides and polysaccharides will be
By the removal of the unfermented di- and 25 converted substantially to glucose which, if de
polysaccharides, either before or‘ after an alkasired after partial or complete neutralization,
line glycerol fermentation, lighter colored slops
are obtained, improved yields of glycerol are se-
may be added toasubsequent mash.
Eiwmllle 2-—IAt the end of an alkaline glycerol
After the addition of the alkaline earth metal
lyzed as in Example 1. The solution remaining
oxide in the speci?ed amount, the mixture will
after removing the strontium oxide-unfermented
show a high alkalinity. Byv reducing this alkg, 40 sugar compound from the fermented mash is con
tially above pH 8.0, but still in the alkaline range,
_acid to a pH value of about 4 and steam-distilled
a considerable increase in insoluble carbohydrate
under reduced pressure- Thereby the glycerol is
compound is obtained. This may be due to the
more readily recovered than without the previous
mutual in?uences on solubility of excess alka- 45 removal of the unfermented sugar,
line earth metal oxides and dissolved polymeric
Example 3-—A slakedlime slurry is added to the
carbohydrate.
\
~
fermented mash of 9. glycerol fermentation. The
This adjustment of the pH can be carried out
solution contains 2% alcohol and about 4% un
by using carbon dioxide gas in such amounts'that
fermented carbohydrate sugars as well as 3%
the alkalinity is lowered to a pH range between 50 glycerine. 40 grams of the slaked lime per liter
7.5 and 8.0.
are added slowly with stirring at a temperature
This additional re oval of carbohydrate from
of 25° C. When the stirring is discontinued after
_
glycerine is to be recovered. A further advan- 55 added to the solution with stirring, and the pH is
tage achieved by this method in the case of ferthereby reduced from about 11 5 to 8 0. The solu
mentation mashes consists in producing solutions
tion ls then ?ltered and about 60% of the unfer
which on concentrating remain clear and do not
merited carbohydrate is removed from the solu
deposit large amounts of insoluble matter
tion The precipitate is acid hydrolyzed with sul
In recovering sugar from a fermented mash by 60 furic acid at pH 0 to 1 and added to a subse
vantageous to precipitate the unfermented sugar
The fermented mash from which the precipitate
prior to recovery of the alcohol contained in the 65 is removed is concentrated and subjected to a
fermentation liquor.
steam distillation for the recovery of glycerol
Example 1.—A wheat mash is used for the pro-
The mash to be fermented may be obtained by
means of dilute mineral acids, as, for example, 70
sulfuiic acid Subsequently the acidity is neutralized by means of lime, forming calcium sulfate, which is separated. Thereafter ?nely
We claim
1. The method of'separating maltose from solu~
tions of sacchari?ed starchy materials containing
the same, compiising adding to such a solution
5 metal oxides and hydroxides at temperatures of
—
2,413,698
6
ing the same, comprising fermenting a solution of
about 0°-40° C. and in quantity suf?cient to pre
cipitate at least a substantial part of the maltose,
mixing the materials and allowing them to stand
until the compound of the metal base with the
maltose begins to settle, removing the insoluble
compound from the solution, and decomposing
the compound by means of a member of the group
consisting of acids and acid anhydrides which
form sparingly soluble salts with the alkaline
earth metal.
‘
2. The method according to claim 1, in which
the pH after precipitating the compound of mal
tose with the alkaline earth base is adjusted to
between about 7.5 and 8.0 before separating the
insoluble compound from the solution. 7
. sacchari?ed starchy material for the production
of glycerol, adding to the fermented solution a
member of the group consisting of alkaline earth
metal oxides and hydroxides at a temperature no
1 higher than about 40° C. and in quantity sufficient
to precipitate at least a substantial part of the
maltose, mixing the materials and allowing them
to stand until the compound of the metal base
with the maltose begins to settle, removing the
10
insoluble compound from the solution, and de
composing the compound by means of a member
of the group consisting of acids and acid anhy
drides which form sparingly soluble salts with the
earth metal.
_
15 alkaline
12. Process according to claim 11, wherein the
3. The method according to‘claim 1, wherein
adding of the alkaline earth metal base is made
after the precipitation of the compound of the ' in the presence of the alcohol formed during the
alkaline earth metal base and the maltose the
fermentation.
pH value is adjusted to between about 7.5 and 8.0
13. The method for the manufacture of glyc
with carbon dioxide gas before separating the in 20 erol which comprises adding to a, maltose-con
taining solution of sacchari?ed starchy materials
soluble compound from the solutio .
4. The method according to clalm 1, in which
a member of the group consisting of alkaline earth
metal oxides and hydroxides at temperatures no
the precipitation of the maltose is carried out in
higher than about 40° C. and in quantity sufficient
the'presence of alcohol.
5. The method of separating maltose from so
to precipitate at least a substantial part of the
maltose, separating the precipitate of the metal
lutions of sacchari?ed starchy materials contain
ing the same, comprising adding to such a solu
base with the maltose, subjecting the residual
tion a member of the group consisting of alkaline
sugar solution to fermentation under alkaline
and hydroxides in quantity suf
conditions, and subsequently distilling glycerol
" earth metal oxides
?cient to precipitate at least a substantial part 30 from the fermented solution.
of the maltose, intimately mixing the materials
14. The method for the manufacture of glyc
erol which comprises fermenting a solution of
to promote reaction, separating the sugar pre
cipitate from the solution, and subsequently de
saccharl?ed starchy material under alkaline con
composing the precipitate to liberate the soluble
ditions and, prior to distillation of the formed
sugars.
6. Method according to claim 5, wherein the
decomposition is effected with the aid of a mem~
ber of the group consisting of acids and acid
glycerol, treating the solution with a metal‘ base
of the group consisting of alkaline earth metal
oxides and hydroxides at a temperature no higher
than about 40° C. and in quantity sufficient to
precipitate‘ at least a substantia1 part of the
maltose, and separating the precipitate of the
anhydrides which form sparingly soluble salts
with the alkaline earth metal.
'7. Method according to claim 5, wherein the
’ metal base with the maltose.
15.‘ The method according to claim 14, wherein
alkaline earth metal compound is calcium oxide.
8. Method according to claim 5, wherein the
the treatment with the alkaline earth metal base
alkaline earth metal compound is strontium oxide.‘
takes place after the fermentation and in the
9. Method according to claim 5, wherein the 45 presence _of the formed alcohol.
’
16. The method according to claim 14, wherein
alkaline earth metal compound is calcium hy
the treatment with the alkaline earth metal base
droxide.
~
'
10. Method according to claim 5, wherein the
takes place at approximately room temperature.
decomposition of the precipitate is effected with 50
dilute sulfuric acid.
11. The method of separating maltose from so
lutions of saccharifled starchy materials contain-l
EDUARD BARBER.
JAMES s. WALLERSTEIN.
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