U.S. patent number RE33,047 [Application Number 07/202,249] was granted by the patent office on 1989-09-05 for process for producing a high-purity maltose.
This patent grant is currently assigned to Kabusihiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo. Invention is credited to Toshio Miyake, Shuzo Sakai, Takashi Shibuya.
United States Patent |
RE33,047 |
Miyake , et al. |
September 5, 1989 |
Process for producing a high-purity maltose
Abstract
High-purity maltose is produced by applying a feed starch sugar
solution with a maltose content of at least 70% to a column packed
with a strongly-acidic cation exchange resin of alkali metal- or
alkaline earth metalform; fractionating the feed solution by
charging water thereto in a high-dextrin fraction, a
high-dextrin.maltose fraction, a high-maltose fraction, a
high-maltose.glucose fraction, and a high-glucose fraction, in the
given order; and recovering the high-maltose fraction. This process
constantly provides a fraction with a maltose content of 93% or
higher, and enables industrial-scale production of a high-purity
maltose much easier and at lower-cost than conventional
processes.
Inventors: |
Miyake; Toshio (Okayama,
JP), Sakai; Shuzo (Okayama, JP), Shibuya;
Takashi (Okayama, JP) |
Assignee: |
Kabusihiki Kaisha Hayashibara
Seibutsu Kagaku Kenkyujo (Okayama, JP)
|
Family
ID: |
14818330 |
Appl.
No.: |
07/202,249 |
Filed: |
June 6, 1988 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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Reissue of: |
402823 |
Jul 28, 1982 |
04487198 |
Dec 11, 1984 |
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Foreign Application Priority Data
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Aug 3, 1981 [JP] |
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56-121725 |
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Current U.S.
Class: |
127/46.3; 127/30;
127/46.2; 435/95 |
Current CPC
Class: |
C07H
3/04 (20130101); C13K 7/00 (20130101) |
Current International
Class: |
C13K
7/00 (20060101); C07H 3/00 (20060101); C07H
3/04 (20060101); C13D 003/14 (); C13K 007/00 () |
Field of
Search: |
;127/46.3,46.2,29,30,32,69 ;435/99,95,100 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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52-46290 |
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Nov 1977 |
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JP |
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55-85395 |
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Jun 1980 |
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JP |
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51-86143 |
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Jul 1986 |
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JP |
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1048 |
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1881 |
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GB |
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1373529 |
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Nov 1974 |
|
GB |
|
1426976 |
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Mar 1976 |
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GB |
|
Primary Examiner: Schor; Kenneth M.
Attorney, Agent or Firm: Browdy and Neimark
Claims
We claim:
1. A process for the separation of maltose from a feed solution by
the utilization of an ion exchange resin, comprising:
(a) providing a feed solution containing at least 70% maltose based
on the weight of the dry solid, the remainder consisting
essentially of glucose and dextrins;
(b) sequentially admitting predetermined volumes of the feed
solution and water to a column of a strongly acidic cation exchange
resin having sulphonyl groups of an alkali metal or alkaline earth
metal form;
(c) sequentially separating the effluents from the column into the
following fractions:
a first fraction rich in dextrins,
a second fraction rich in dextrins, but highly contaminated with
maltose,
a third fraction of substantially pure maltose,
a fourth fraction rich in maltose, but highly contaminated with
glucose, and
a fifth fraction rich in glucose;
(d) recovering the third fraction of substantially pure
maltose;
(e) sequentially admitting into the column;
the second fraction obtained in the step (c),
a feed solution having a maltose content of at least 70% based on
the weight of dry solid, and the remainder consisting essentially
of glucose and dextrin,
the forth fraction obtained in the step (c), and water; and
(f) repeating steps (c), (d) and (e) in a cyclic manner.
2. A process in accordance with claim 1, wherein the maltose
content in the third fraction is 93% or higher, based on the weight
of the dry solid.
3. A process in accordance with claim 1, wherein the bed depth of
the column is at least 7 m.
4. A process in accordance with claim 1, wherein the temperature of
the column of the resin is kept at 45.degree.-85.degree. C.
5. A process in accordance with claim 1, wherein the cation
exchange resin is in the form of N.sup.+, K.sup.+, Ca.sup.2+, or
Mg.sup.2+.
6. A process in accordance with claim 1, wherein the concentration
of the dry solid solute in the feed solution is in the range of
10-70 w/w %.
7. A process in accordance with claim 1, wherein the water is
admitted to the column at a flow rate of SV 0.1-2.0.
Description
BACKGROUND OF THE INVENTION
The present invention relates to a process for producing a
high-purity maltose.
Recently, various advantages of maltose in food products and
pharmaceuticals have been established one after another. Thus it
uses have expanded rapidly. These expanded uses have inevitably led
to increasing demands for a high-purity maltose.
Conventionally, maltose, has been available as a saccharified
starch product with a maltose content of about 40-50 w/w % based
upon the weight of the dry solid solute (all percentages are used
in the specification mean "weight percentages on dry solid basis"
unless otherwise specified) which is obtainable by subjecting a
liquefied starch solution to the action of a malt enzyme.
Recent advances in starch saccharifiction techniques have somewhat
simplified the production of a saccharified starch product with a
maltose content of 50% or higher, for example, by the combined
treatment of starch with .beta.-amylase and starch debranching
enzyme.
The above described starch saccharification technique, however,
from economical and technical standpoints, renders the direct
production of a high-purity maltose with a maltose content of 90%
or higher very difficult.
Some processes for obtaining a high-purity maltose are disclosed in
recent patent applications. In some of these process, a starch
sugar solution containing maltose is passed through a column of an
anion exchange resin. For example, Japanese Patent Publication No.
46,290/77 discloses a process for producing a high-purity maltose
comprising preparing a starch sugar solution substantially
consisting of dextrin and about 65% maltose, and applying the
solution to an anion exchange resin of OH-form to adsorb the
maltose constituent and also to remove the dextrin constituent.
Since, however, in such a process the maltose constituent is
adsorbed on the anion exchange resin of OH-form, the solution
should be applied to the resin at the lowest possible temperature,
preferably, below 20.degree. C., to prevent the isomerization of
the maltose constituent. Thus, increased viscosity and microbial
contamination as well as low purification capability result,
rendering its industrial-scale practice very difficult. Further,
Japanese Patent Publication No. 20,579/79 discloses a process for
producing a high-purity maltose which comprises applying a starch
sugar solution, containing glucose and maltose, to a column packed
with an anion exchange resin of SO.sub.3.sup.2- - or SO.sub. 3
H.sup.- -form, to fractionate the solution into the glucose- and
maltose-constituents. The process is, however, inadequate as a
process for industrial-scale production of a high-purity maltose
because the bonding of the SO.sub.3.sup.2- - or SO.sub.3 H.sup.-
-group is labile.
SUMMARY OF THE INVENTION
The present inventors have investigated processes for producing a
high-purity maltose using a strongly-acidic cation exchange resin,
more particularly, of alkali metal- or alkaline earth metal-form,
instead of an anion exchange resin which has the above described
disadvantages. These efforts resulted in the finding that a
high-purity maltose is easily obtainable by admitting a feed starch
sugar solution with a maltose content of at least 70% and water to
a column packed with a strongly-acidic cation exchange resin of
alkali metal- or alkaline earth metal-form thereby fractionating
the solution into a high-dextrin fraction, a high-dextrin, maltose
fraction, a high-maltose fraction, a high-maltose.glucose fraction,
and a high-glucose fraction (the terms "high-A fraction" and
"high-A.B fraction" as used in the specification shall mean the
eluted fractions rich in A, or rich in A but highly contaminated
with B); and recovering the high-maltose fraction.
Also, these efforts have resulted in the additional finding that
high-purity maltose is constantly obtainable in higher
concentration and at higher recovery yield by employing a method
where the feed starch sugar solution is applied to the column
together with the previously obtained high-dextrin.maltose- and/or
high-maltose.glucose-fractions, and wherein the resultant
high-dextrin.maltose-and/or high-maltose.glucose fractions are
admitted to the column together with a fresh feed starch sugar
solution in the next fractionation step.
BRIEF DESCRIPTION OF THE DRAWING
The drawing shows the elution pattern of the feed solution upon the
fractionation into fractions A through E, i.e., the high-dextrin
fraction, high-dextrin.maltose fraction, high-maltose fraction,
high-maltose.glucose fraction, and high-glucose fraction,
respectively.
The above described findings led to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The feed starch sugar solution usable in the present invention may
be almost any substantially-ketose-free solution of aldoses derived
from starch. Such a feed solution results in a high-maltose
fraction; and with a maltose content of 90%, typically 93% or
higher, in a high yield when subjected to the fractionation
according to the present invention. For example, feed starch sugar
solution may be a saccharified starch solution obtained by
subjecting starch to the actions of starch-degrading enzymes, e.g.,
.alpha.- and .alpha.-amylases, and starch-debranching enzyme, or
may be an aqueous solution of a commercially-available starch sugar
product having a maltose content of at least 70%.
The strongly-acidic cation exchange resin of alkali metal- or
alkaline earth metal-form usable in the invention may be, for
example, one or more members of styrene-divinylbenzene copolymer
resins bearing sulphonyl groups of alkali metal- or alkaline earth
metal-form, such as Na.sup.+, K.sup.+, Ca.sup.2+, or Mg.sup.2+.
Commercially-available resins are, for example, "Dowex 50WX2",
"Dowex 50WX4", and "Dowex 50WX8", products of Dow Chemical Company,
Midland, Mich., U.S.A., "Amberlite CG-120", a product of Rohm &
Haas Company, Philadelphia, Pa. , U.S.A., "XT-1022E", a product of
Tokyo Chemical Industries, Kita-ku, Tokyo, Japan, and "Diaion SK
1B", "Diaion SK 102", and "Diaion SK 104", products of Mitsubishi
Chemical Industries Limited, Tokyo, Japan. All of these resins have
excellent fractionating capability to obtain the high-maltose
fraction, and are highly heat- and abrasion-resitant. Thus, they
are advantageously useful for producing a high-purity maltose on an
industrial-scale.
In the process according to the present invention, a resin with a
nominal particle size of about 0.01-0.5 mm is packed in one or more
columns. The bed depth preferred in the invention is generally 7 m
or longer. If two or more columns are used, they are cascaded to
give a total bed depth of 7 m or longer.
As to the column usable in the present invention, any column can be
used regardless of its material, size, and shape so far as the
objectives of the invention can be attained therewith. The column
may be, for example, of glass, plastic or stainless steel, and its
shape may be, for example, in cylindrical or square pillar form,
but it should be designed to give the most effective laminar flow
possible when the feed starch sugar solution is applied to the
column packed with the resin.
The following description concretely explains in detail the method
of the present invention.
One or more column(s) is packed with a strongly-acidic cation
exchange resin of alkali metal- or alkaline earth metal-form, in an
aqueous suspension, to give a total bed depth of 7 m or longer.
While keeping the temperature in the column(s) at
45.degree.-85.degree. C., the feed starch sugar solution, at a
concentration of about 10-70 w/w %, in an amount of about 1-60 v/v
% against the bed volume, is admitted into the column(s) and then
charged upwards or downwards with water at a flow rate of about SV
0.1-2.0 to effect fractionation of the material starch sugar
solution into a high-dextrin fraction, a high-dextrin.-maltose
fraction, a high-maltose fraction, a high-maltose.glucose fraction,
and a high-glucose fraction, in the given order. The high
maltose-fraction is then recovered.
Although the eluted fractions are generally collected in about 1-20
v/v % against the bed volume, they may be distributed automatically
into the fractions.
When the feed starch sugar solution is admitted into the column
prior to, after, or together with the previously obtained
high-dextrin.maltose- and/or high-maltose.glucose-fractions, the
amount of water required for substantial fractionation of the feed
starch sugar solution can be sharply reduced, and the maltose
constituent in the solution can be recovered in higher purity,
higher concentration, and higher yield. Preferably, the previously
obtained high-dextrin.maltose fraction, the feed starch sugar
solution, and the previoiusly obtained high-maltose.glucose
fraction are applied successively to the column in the given
order.
Although the high-maltose fraction thus obtained can be used
intact, it may be, if necessary, treated further as follows. The
high-maltose fraction may be subjected to conventional purification
steps, e.g., filtration, decolorization and/or deionization. Then,
the purified product is, for example, concentrated to obtain a
syrup, or crystallized to obtain a mascuit which may be spray-dried
into crystalline powder, or separated into mother liquor and
maltose crystals of much higher purity.
The high-purity maltose thus obtained is extremely useful in
various applications, e.g., for production of food products or
pharmaceuticals.
The following experiments explain the present invention in more
detail.
EXPERIMENT 1
Feed starch sugar solution
The feed starch sugar solutions used in this experiment were
prepared from commercially-available starch sugar products as
listed in Table I, products of Hayashibara Company, Limited,
Okayama, Japan, by dissolving or diluting them in water to give
respective concentrations of 45 w/w %.
"Dowex 50WX4 (NA.sup.+)", a commercially-available strongly-acidic
cation exchange resin of alkali metal-form, a product of Dow
Chemical Company, Midland, Mich., U.S.A., in an aqueous suspension,
was packed in a jacketted stainless steel column, inside diameter,
5.4 cm, to give a bed depth of 10 m.
While keeping the temperature in the column at 75.degree. C., each
feed starch sugar solution listed in Table I was admitted to the
column in an amount of 5 v/v % against the bed volume, and
fractionated by charging 75.degree. C. hot water at a flow rate of
SV 0.4 through the column and the high-maltose fraction, with a
maltose content of 93 % or higher, was recovered. The results are
given in Table II.
The experimental results, as shown in Table II, confirm that when
the maltose content in the feed starch sugar solution is 70% or
higher, a high-maltose fraction with a maltose content of 93% or
higher is easily obtainable in an extremely high yield, i.e. 80% or
higher, against the maltose constituent in the feed starch sugar
solution.
TABLE I ______________________________________ Sugar composition
(%) A B C D ______________________________________ Maltrup 7.1 48.0
44.9 Malstar 3.2 66.0 30.8 HM-75 1.0 76.8 22.2 Sunmalt 4.3 85.0
10.7 Maltose H 0.6 91.5 7.9 ______________________________________
Note: A is the material starch sugar solution (trade name or
Registered Trade Mark); B, glucose; C, maltose; and D, maltotriose
and higher oligosaccharides.
TABLE II ______________________________________ A B C D E
______________________________________ Maltrup 48.0 132.2 44.2
control Malstar 66.0 231.7 56.3 control HM-75 76.8 403.6 84.3
present invention Sunmalt 85.0 483.8 91.3 present invention Maltose
H 91.5 548.8 96.2 present invention
______________________________________ Note: A is the material
starch sugar solution (trade name or Registered Trade Mark); B,
maltose content in the feed starch sugar solution (%); C, maltose
yield in the highmaltose-fraction (g); D, maltose yield against the
maltose constituent in the feed starch sugar solution (%); and E,
remarks.
EXPERIMENT 2
Bed depth
Similarly as in Experiment 1, the strongly-acidic cation exchange
resin of alkali metal-form was packed in one or two columns to give
respective total bed depths in the range of 1-20 m as in Table
III.
While keeping the temperature in the columns of different bed
depths at 75.degree. C., 45 w/w % aqueous solution aliquots of
"Sunmalt", a commercially-available starch sugar powder with a
maltose content of 85.0%, Registered Trade Mark of Hayashibara
Company, Limited, Okayama, Japan, were admitted to the columns in
an amount of 5 v/v % against the bed volume, and then fractionated
by charging 75.degree. C. hot water at a flow rate of SV 0.4
through the column and the high-maltose fraction, with a maltose
content of 93% or higher, was recovered. The results are given in
Table III.
The experimental results, as shown in Table III, confirm that when
the bed depth is 7 m or longer, a high-maltose fraction with a
maltose content of 93% or higher is easily obtainable in an
extremely high yield, i.e., 80% or higher, against the maltose
constituent in the feed starch solution.
TABLE III ______________________________________ A B C D E
______________________________________ 1 1 114.5 30.1 56.9 3 1
343.5 102.1 64.2 5 1 572.5 192.9 72.8 7 1 801.5 324.9 87.6 10 1
1145.0 483.8 91.3 15 1 1715.5 739.3 93.0 20 2.sup.6 2290.0 994.1
93.8 ______________________________________ Note: A is total bed
depth (m); B, number of columns; C, amount of the feed starch sugar
solution applied (ml); D, maltose yield in the highmaltose fraction
(g); E, maltose yield against the maltose constituent in the fee
starch sugar solution (%); and .sup.6 means two columns were
cascaded.
EXPERIMENT 3
Fractionation temperature
After packing, the strongly-acidic cation exchange resin of alkali
metal-form in columns to give respective bed depths of 10 m, as in
Experiment 1, feed starch sugar solution aliquots, prepared
similarly as in Experiment 2, were applied thereto, and
fractionated similarly as in Experiment 1, except that the columns
were kept at different temperatures in the range of
35.degree.-95.degree. C. during the fractionation. The high-maltose
fraction, with a maltose content of 93% or higher, was recovered.
The results are given in Table IV.
The experimental results, as shown in Table IV, confirm that when
the column is kept at a temperature in the range of
45.degree.-85.degree. C.,a high-maltose fraction with a maltose
content of 93% or higher is easily obtainable in an extremely high
yield, i.e., 80% or higher, against the maltose constituent in the
feed starch sugar solution with less browning.
TABLE IV ______________________________________ A B C D E
______________________________________ 35 374.7 70.7 0.023 easy 45
430.2 81.2 0.059 easy 55 471.1 88.9 0.105 easy 65 476.9 90.0 0.150
easy 75 483.8 91.3 0.176 easy 85 485.9 91.7 0.205 easy 95 472.2
89.1 0.496 difficult ______________________________________ Note: A
is the fractionation temperature (.degree.C.); B total yield of
sugar constituents with a maltose content of 93% or higher (g); C,
maltose yiel against the maltose constituent in the feed starch
sugar solution (%); D, colorization degree, obtained by measuring
the absorbance of the highmaltose fraction in 10 cm cell
(A.sub.420nm- A.sub.720 nm), and reducing the obtained value into
that in 30 w/w % solution, and E, decolorization using 0.1%
activated carbon against sugar constituen ts.
Several embodiments of the invention are disclosed hereinafter.
EXAMPLE 1
A feed starch sugar solution was prepared by diluting "HM-75",
trade name of a commercially-available starch sugar syrup with a
maltose content of 76.8%, a product of Hayashibara Company,
Limited, Okayama, Japan, in water to give a concentration of 45 w/w
%.
"XT-1022E (Na.sup.+)", a commercially-available strongly-acidic
cation exchange resin of alkali metal-form, a product of Tokyo
Chemical Industries, Kita-ku, Tokyo, Japan, in an aqueous
suspension, was packed in four jacketted stainless steel columns,
inside diameter, 5.4 cm, to give respective bed depths of 5 m, and
the columns were cascaded to give a total bed depth of 20 m.
While keeping the temperature in the columns at 55.degree. C., the
feed starch sugar solution was admitted thereto in an amount of 5
v/v % against the bed volume, and then fractionated by charging
55.degree. C. hot water at a flow rate of SV 0.13 through the
columns and the high-maltose fraction, with a maltose content of
93% or higher, was recovered.
The high-maltose fraction contained 808.2 g maltose, and the yield
was extremely high, i.e., 84.3%, against the maltose constituent in
the feed starch sugar solution.
EXAMPLE 2
A feed starch sugar solution was prepared by dissolving "Sunmalt",
a commercially-available starch sugar powder with a maltose content
of 85.0%, Registered Trade Mark of Hayashibara Company, Limited,
Okayama, Japan, in water to give a concentration of 60 w/w %.
The resin, used in Example 1, was converted into K.sup.+ -form in
the usual way and packed in a jacketted stainless steel column,
inside diameter, 2.2 cm, to give a bed depth of 10 m.
While keeping the temperature in the column at 60.degree. C., the
feed starch sugar solution was admitted thereto in an amount of 3
v/v % against the bed volume, and then fractionated by charging
60.degree. C. hot water at a flow rate of SV 0.2 through the column
and the high-maltose fraction, with a maltose content of 93% or
higher, was recovered.
The high-maltose fraction contained 65.7 g maltose, and the yield
was extremely high, i.e., 88.3% against the maltose constituent in
the feed starch sugar solution.
EXAMPLE 3
A feed starch sugar solution was prepared by dissolving "Sunmalt",
a commercially-available starch sugar powder with a maltose content
of 85.0%, Registered Trade Mark of Hayashibara Company, Limited,
Okayama, Japan, in water to give a concentration of 45 w/w %.
"Dowex 50WX4 (Mg.sup.2+)", a commercially-available strongly-acidic
cation exchange resin of alkaline earth metal-form, a product of
Dow Chemical Company, Midland, Mich., U.S.A., in an aqueous
suspension, was packed in fresh columns of the same material and
dimensions as used in Example 1 to give a total bed depth of 15
m.
While keeping the temperature in the columns at 75.degree. C., the
feed starch sugar solution was applied thereto in an amount of 6.6
v/v % against the bed volume, and then fractionated by charging
75.degree. C. hot water at a flow rate of SV 0.13 through the
columns and the high-maltose fraction, with a maltose content of
93% or higher, was recovered.
The high-maltose fraction contained 913.7 g maltose, and the yield
was extremely high, i.e., 87.1%, against the maltose constituent in
the feed starch sugar solution.
EXAMPLE 4
In this example, a dual-stage fractionation was carried out.
The first fractionation was carried out as follows. Similarly as in
Example 1, a feed starch sugar solution was applied to a column,
and fractionated except that the feed starch sugar solution was
applied to the column in an amount of 20 v/v % against the bed
volume. The elution pattern is given in the drawing, where
Fractions A through E show a high-dextrin fraction, a
high-dextrin.maltose fraction, a high-maltose fraction, a
high-maltose.glucose fraction, and a high-glucose fraction
respectively, and where the elution is effected in the given order.
Fraction C, the high-maltose fraction, was recovered, and Fractions
A and E were removed from the fractionation system.
The additional fractionation was carried out as follows. Fraction
B, the feed starch sugar solution in an amount of about 10 v/v %
against the bed volume, and Fraction D were admitted into the
column successively in the given order, and the column then charged
with 75.degree. C. hot water, as in Example 3, to effect
fractionation. The high maltose fractions, with a maltose content
of 94%, were recovered. The additional fractionation was repeated
up to 30 batches in total, and the averaged results per batch were
calculated. On an average, one high-maltose fraction contained 1483
g maltose, and the yield was extremely high, i.e., 93.3%, against
the maltose constituent in the feed starch sugar solution.
EXAMPLE 5
A feed starch sugar solution was prepared by dissolving "Maltose
H", trade name of a commercially-available starch sugar powder with
a maltose content of 91.5%, a product of Hayashibara Company,
Limited, Okayama, Japan, in water to give a concentration of 45 w/w
%.
"Amberlite CG-120 (Ca.sup.2+)", a commercially-available
strongly-acidic cation exchange resin of alkaline earth metal-form,
a product of Rohm & Haas Company, Philadelphia, Pa., U.S.A.,
was packed in fresh columns of the same material and dimensions as
used in Example 1 to give a total bed depth of 10 m.
Also, in this Example, a dual-stage fractionation was carried out.
The first fractionation was carried out as follows. While keeping
the temperature in the columns at 80.degree. C., the feed starch
sugar solution was applied thereto in an amount of 20 v/v % against
the bed volume, and then fractinated by charging 80.degree. C. hot
water at a flow rate of SV 0.6 through the columns to obtain a
similar elution pattern as in Example 4. Similarly as in Example 4,
Fraction C, the high-maltose fraction, was harvested, and Fractions
A and E were removed from the fractionation system.
The additional fractionation was carried out as follows. Fraction
B, the feed starch sugar solution in an amount of 10 v/v % against
the bed volume, and Fraction D, were admitted into the column
successively in the given order, and the column then charged with
80.degree. C. hot water at a flow rate of SV 0.6 to effect
fractionation. The resultant high-maltose fractions, with a maltose
content of 96% or higher, was recovered. The additional
fractionation was repeated up to 100 batches in total, and the
averaged results per batch were calculated. On an average, one
high-maltose fraction contained 1084 g maltose, and the yield was
extremely high, i.e., 95%, against the maltose constituent in the
feed starch sugar solution.
* * * * *