U.S. patent application number 09/883218 was filed with the patent office on 2002-02-07 for method for recovering amino acids.
This patent application is currently assigned to NIPPON BEET SUGAR MFG. CO., LTD. Invention is credited to Aritsuka, Tsutomu, Kanno, Takashi, Kikuchi, Hiroto, Sayama, Koji.
Application Number | 20020016502 09/883218 |
Document ID | / |
Family ID | 26596751 |
Filed Date | 2002-02-07 |
United States Patent
Application |
20020016502 |
Kind Code |
A1 |
Kanno, Takashi ; et
al. |
February 7, 2002 |
Method for recovering amino acids
Abstract
A method for recovering amino acids, which comprises supplying a
mixed solution containing inorganic acid salts, amino acids and
non-electrolytes such as saccharides to a first-step resin layer
comprising an Na type or K type strongly acidic ion exchange resin;
separating an effluent into at least a first fraction containing
coloring matters, acidic amino acids and ashes, a second fraction
containing neutral amino acids and saccharides, and a third
fraction containing betaines; supplying the second fraction to a
second-step resin layer comprising at least one resin selected from
the group consisting of NH.sub.4 type, Ca type and Mg type strongly
acidic ion exchange resins, and optionally further supplying it to
a third-step resin layer comprising an Mg type or Ca type strongly
acidic ion exchange resin different from the resin of the
second-step resin layer, thereby recovering various kinds of amino
acids contained in an effluent.
Inventors: |
Kanno, Takashi; (Hokkaido,
JP) ; Sayama, Koji; (Hokkaido, JP) ; Aritsuka,
Tsutomu; (Hokkaido, JP) ; Kikuchi, Hiroto;
(Hokkaido, JP) |
Correspondence
Address: |
SUGHRUE, MION, ZINN
MACPEAK & SEAS, PLLC
2100 Pennsylvania Avenue, NW
Washington
DC
20037-3213
US
|
Assignee: |
NIPPON BEET SUGAR MFG. CO.,
LTD
|
Family ID: |
26596751 |
Appl. No.: |
09/883218 |
Filed: |
June 19, 2001 |
Current U.S.
Class: |
562/443 ;
548/339.1; 548/497; 548/530; 562/516 |
Current CPC
Class: |
C12P 13/22 20130101;
C12P 13/04 20130101; C12P 13/06 20130101; C12P 13/225 20130101;
C12P 13/005 20130101; C12P 13/08 20130101 |
Class at
Publication: |
562/443 ;
548/339.1; 548/497; 548/530; 562/516 |
International
Class: |
C07C 227/38; C07D
209/20 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 21, 2000 |
JP |
2000-226111 |
Jun 30, 2000 |
JP |
2000-237745 |
Claims
What is claimed is:
1. A method for recovering amino acids, which comprises supplying a
mixed solution containing inorganic acid salts, coloring matters,
ashes, betaines, amino acids and non-electrolytes including
saccharides to a first resin layer comprising a sodium type
strongly acidic ion exchange resin or a potassium type strongly
acidic ion exchange resin; separating an effluent which flows out
of the first resin layer using water or an aqueous solution of
caustic alkali as an eluent into at least a first fraction
containing coloring matters, acidic amino acids and ashes, a second
fraction containing neutral amino acids and saccharides, and a
third fraction containing betaines; supplying the second fraction
to a second resin layer comprising an ammonium type strongly acidic
ion exchange resin to allow the neutral amino acids to be adsorbed
by the second resin layer; and recovering an effluent which flows
out of the second resin layer using an aqueous solution of ammonia
as an eluent, thereby recovering tyrosine and a mixture of the
neutral amino acids contained in the effluent.
2. A method for recovering amino acids, which comprises supplying a
mixed solution containing inorganic acid salts, coloring matters,
ashes, betaines, amino acids and non-electrolytes including
saccharides to a first resin layer comprising a sodium type
strongly acidic ion exchange resin or a potassium type strongly
acidic ion exchange resin; separating an effluent which flows out
of the first resin layer using water or an aqueous solution of
caustic alkali as an eluent into at least a first fraction
containing coloring matters, acidic amino acids and ashes, a second
fraction containing amino acids and saccharides, and a third
fraction containing betaines; supplying the second fraction to a
third resin layer comprising a calcium type strongly acidic ion
exchange resin; and separating an effluent which flows out of the
third resin layer using water as an eluent into at least a first
fraction containing saccharides, amino acids and ashes, and a
second fraction containing neutral amino acids including tyrosine,
thereby recovering tyrosine and a mixture of the neutral amino
acids contained in the effluent.
3. A method for recovering amino acids, which comprises supplying a
mixed solution containing inorganic acid salts, coloring matters,
ashes, betaines, amino acids and non-electrolytes including
saccharides to a first resin layer comprising a sodium type
strongly acidic ion exchange resin or a potassium type strongly
acidic ion exchange resin; separating an effluent which flows out
of the first resin layer using water or an aqueous solution of
caustic alkali as an eluent into at least a first fraction
containing coloring matters, acidic amino acids and ashes, a second
fraction containing amino acids and saccharides, and a third
fraction containing betaines, supplying the second fraction to a
third resin layer comprising a calcium type strongly acidic ion
exchange resin; and separating an effluent which flows out of the
third resin layer using water as an eluent into at least a first
fraction containing saccharides, amino acids and ashes, a second
fraction containing .gamma.-amino butyric acid, alanine and valine,
a third fraction containing serine and valine, and a fourth
fraction containing leucine, isoleucine and tyrosine, thereby
recovering at least one selected from the group consisting of
.gamma.-amino butyric acid, alanine, valine, serine, leucine,
isoleucine and tyrosine contained in the effluent.
4. The method according to claim 3, wherein neutral amino acids
containing .gamma.-amino butyric acid, alanine and valine is
recovered from the second fraction of the effluent which flows out
of said third resin layer.
5. The method according to claim 3, wherein the second fraction of
the effluent which flows out of said third resin layer is further
supplied to a fourth resin layer comprising a magnesium type
strongly acidic ion exchange resin, and an effluent which flows out
of the fourth resin layer using water as an eluent is separated
into at least a first fraction containing .gamma.-amino butyric
acid and a second fraction containing alanine, valine and serine,
thereby recovering .gamma.-amino butyric acid and at least one
selected from the group consisting of alanine, valine and
serine.
6. The method according to claim 3, wherein neutral amino acids
containing serine and valine is recovered from the third fractions
of the effluent which flows out of said third resin layer.
7. The method according to claim 3, wherein the third fractions of
the effluent which flows out of said third resin layer is further
supplied to a fourth resin layer comprising a magnesium type
strongly acidic ion exchange resin, and an effluent which flows out
of the fourth resin layer using water as an eluent is separated
into at least a first fraction containing serine, a second fraction
containing valine and a third fraction containing the other neutral
amino acids, thereby recovering serine, valine, and the other
neutral amino acids.
8. The method according to claim 3, wherein at least one selected
from the group consisting of tyrosine, leucine and isoleucine are
recovered from the fourth fraction of the effluent which flows out
of said third resin layer.
9. A method for recovering amino acids, which comprises supplying a
mixed solution containing inorganic acid salts, coloring matters,
ashes, betaines, amino acids and non-electrolytes including
saccharides to a first resin layer comprising a sodium type
strongly acidic ion exchange resin or a potassium type strongly
acidic ion exchange resin; separating an effluent which flows out
of the first resin layer using water or an aqueous solution of
caustic alkali as an eluent into at least a first fraction
containing coloring matters, acidic amino acids and ashes, a second
fraction containing amino acids and saccharides, and a third
fraction containing betaines; supplying the second fraction to a
fourth resin layer comprising a magnesium type strongly acidic ion
exchange resin; and separating an effluent which flows out of the
fourth resin layer using water as an eluent into at least a first
fraction containing saccharides, amino acids and ashes, and a
second fraction containing neutral amino acids including tyrosine,
thereby recovering tyrosine and a mixture of the neutral amino
acids contained in the effluent.
10. A method for recovering amino acids, which comprises supplying
a mixed solution containing inorganic acid salts, coloring matters,
ashes, betaines, amino acids and non-electrolytes including
saccharides to a first resin layer comprising a sodium type
strongly acidic ion exchange resin or a potassium type strongly
acidic ion exchange resin; separating an effluent which flows out
of the first resin layer using water or an aqueous solution of
caustic alkali as an eluent into at least a first fraction
containing coloring matters, acidic amino acids and ashes, a second
fraction containing amino acids and saccharides, and a third
fraction containing betaines, supplying the second fraction to a
fourth resin layer comprising a magnesium type strongly acidic ion
exchange resin; and separating an effluent which flows out of the
fourth resin layer using water as an eluent into at least a first
fraction containing saccharides, amino acids and ashes, a second
fraction containing serine, a third fraction containing alanine and
valine, and a fourth fraction containing tyrosine, leucine,
isoleucine and .gamma.-amino butyric acid, thereby recovering at
least one selected from the group consisting of serine, alanine,
valine, tyrosine, leucine, isoleucine and .gamma.-amino butyric
acid contained in the effluent.
11. The method according to claim 10, wherein neutral amino acids
containing alanine and valine is recovered from the third fraction
of the effluent which flows out of said fourth resin layer.
12. The method according to claim 10, wherein the third fraction of
the effluent which flows out of said fourth resin layer is further
supplied to a third resin layer comprising a calcium type strongly
acidic ion exchange resin, and an effluent which flows out of the
third resin layer using water as an eluent is separated into at
least a first fraction containing alanine, a second fraction
containing valine, and a third fraction containing the other
neutral amino acids, thereby recovering alanine, valine and the
other neutral amino acids.
13. The method according to claim 10, wherein the fourth fraction
of the effluent which flows out of said fourth resin layer is
further supplied to a third resin layer comprising a calcium type
strongly acidic ion exchange resin, and an effluent which flows out
of the third resin layer using water as an eluent is separated into
at least a first fraction containing .gamma.-amino butyric acid,
and a second fraction containing tyrosine, leucine and isoleucine,
thereby recovering .gamma.-amino butyric acid and at least one
selected from the group consisting of tyrosine, leucine and
isoleucine.
14. The method according to any one of claims 1 to 13, wherein an
aqueous solution of caustic alkali having a pH of 8.5 to 11.0 is
used as the eluent for said first resin layer.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a method for recovering
various kinds of amino acids from a mixed solution comprising
inorganic acid salts, coloring matters, ashes, betaines, amino
acids and non-electrolytes such as saccharides. In the course of
producing sucrose from sugar beets, impurities other than sucrose
move into molasses. The molasses still contains sucrose in about a
half amount, so that sucrose has further been recovered from the
molasses by ion chromatography (hereinafter also referred to as
"CR") Residues containing sucrose which can not be recovered and
trace amounts of amino acids have been treated as "CR waste
liquor". Further, in the production of sucrose, when ion exchange
resins used for purification of sugar liquid in the process of
sugar manufacture are regenerated, trace amounts of amino acids
adsorbed by the ion exchange resins are eliminated together with
regenerating solutions to flow out. This effluent liquor has also
been treated as "resin waste liquor". These CR waste liquor and
resin waste liquor have hitherto been subjected to the activated
sludge process and discarded, or only condensed for utilization as
organic fertilizer. The present invention relates to a novel method
for recovering amino acids, which makes it possible to recover
trace amounts of amino acids existing in such waste liquor.
BACKGROUND OF THE INVENTION
[0002] Previously, CR has been utilized as one method for
separating respective ingredients from solutions containing the
multiple ingredients, such as natural material solutions. However,
it has been practically impossible to industrially utilize CR as
such for separating trace amounts of ingredients, considering the
price of products obtained. Because it necessitates large-scale
equipment and a large amount of treating liquid. Many processes
have been therefore contrived for industrially using CR. For
example, the present inventors have disclosed in Japanese Patent
Publication No. 56-39640 that only fractions having
sucrose/raffinose ratios within a specific range are collected by
separation through a salt type strongly acidic ion exchange resin,
and fractionally crystallized, which makes it possible to
industrially produce raffinose from sugar beet molasses. Further,
as to a method for separating materials similar to those in the
present invention, one invention is disclosed in Japanese Patent
Laid-Open Publication (Hei) 6-276995. This invention is directed to
a method for producing a raw flavoring material, which comprises
supplying CR waste liquor or resin waste liquor to a sodium type
strongly acidic ion exchange resin to allow amino acids to be
adsorbed thereby, and then, eluting them with a solution of sodium
hydroxide through a hydrogen ion type weakly acidic ion exchange
resin connected to the back of the sodium type strongly acidic ion
exchange resin.
[0003] The object of the invention described in Japanese Patent
Laid-Open Publication (Hei) 6-276995 is to obtain an amino
acid-rich fraction, and the fraction can be used as a raw flavoring
material. However, the fraction contains materials other than amino
acids, and this invention is not directed to a method for
recovering only amino acids.
SUMMARY OF THE INVENTION
[0004] An object of the present invention is to provide a method
for recovering various kinds of amino acids from a solution
containing trace amounts of amino acids in a highly concentrated
inorganic acid salt or a highly concentrated non-electrolyte such
as saccharide, for example, CR waste liquor or resin waste
liquor.
[0005] The present invention relates to a method for recovering
amino acids, which comprises (1) supplying a mixed solution
containing inorganic acid salts, coloring matters, ashes, betaines,
amino acids and non-electrolytes such as saccharides to a
first-step first resin layer comprising a sodium type strongly
acidic ion exchange resin (hereinafter also referred to as an "Na
type IER") or a potassium type strongly acidic ion exchange resin
(hereinafter also referred to as a "K type IER"), (2) separating an
effluent which flows out of the first resin layer using water or an
aqueous solution of a caustic alkali as an eluent into at least a
first fraction containing coloring matters, acidic amino acids and
ashes, a second fraction containing neutral amino acids and
saccharides, and a third fraction containing betaines, (3)
supplying the second fraction to a second-step resin layer
comprising at least one resin selected from the group consisting of
an ammonium type strongly acidic ion exchange resin (hereinafter
also referred to as an "NH.sub.4 type IER"), a calcium type
strongly acidic ion exchange resin (hereinafter also referred to as
a Ca type IER") and a magnesium type strongly acidic ion exchange
resin (hereinafter also referred to as an Mg type IER"), and (4)
recovering various kinds of amino acids contained in an effluent
which flows out of the second-step resin layer.
[0006] In the present invention, the term "neutral amino acids"
means neutral amino acids including neutral aromatic amino acids
such as tyrosine, in a broad sense.
[0007] Also, in the present invention, the term "a caustic alkali"
means alkali hydroxide including sodium hydroxide and potassium
hydroxide.
[0008] As to an eluent used for the ion exchange resin in the
present invention, an aqueous solution of ammonia is used for the
NH.sub.4 type IER, water or an aqueous solution of a caustic alkali
for the Na type or K type IER, and water for the Ca type IER and
the Mg type IER.
[0009] Further, when the above-mentioned second-step resin layer is
the Ca type IER, the effluent which flows out of the second-step
resin layer may be further partly supplied to a third-step resin
layer comprising the Mg type IER to recover various kinds of amino
acids contained in an effluent which flows out of the third-step
resin layer using water as an eluent (which means "recovering
method 2-2-A" described later).
[0010] Furthermore, when the above-mentioned second-step resin
layer is the Mg type IER, the effluent which flows out of the
second-step resin layer may be further partially supplied to a
third-step resin layer comprising the Ca type IER to recover
various kinds of amino acids contained in an effluent which flows
out of the third-step resin layer using water as an eluent (which
means "recovering method 3-2-A" described later).
[0011] As the eluent for the above-mentioned first resin layer,
there may be used an aqueous solution of a caustic alkali having a
pH of 8.5 to 11.0.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 is a graph showing a relationship between respective
fractions which flow out of a first-step first resin layer and
concentrations of respective ingredients contained in an
effluent;
[0013] FIG. 2 is a graph showing a relationship between respective
fractions which flow out of a first-step first resin layer and
concentrations of respective amino acids based on the total amino
acids contained in an effluent;
[0014] FIG. 3 is a graph showing a relationship between respective
fractions which flow out of a second-step third resin layer and
concentrations of saccharides, amino acids and ashes contained in
an effluent;
[0015] FIG. 4 is a graph showing a relationship between respective
fractions which flow out of a second-step third resin layer and
concentrations of respective amino acids based on the total amino
acids contained in an effluent;
[0016] FIG. 5 is a graph showing a relationship between respective
fractions of a GABA(.gamma.-amino butyric acid)-rich fraction which
flows out of a third-step fourth resin layer and concentrations of
respective amino acids based on the total amino acids contained in
an effluent;
[0017] FIG. 6 is a graph showing a relationship between respective
fractions of a valine-rich fraction which flows out of a third-step
fourth resin layer and concentrations of respective amino acids
based on the total amino acids contained in an effluent;
[0018] FIG. 7 is a graph showing a relationship between respective
fractions which flow out of a second-step fourth resin layer and
concentrations of saccharides, amino acids and ashes contained in
an effluent;
[0019] FIG. 8 is a graph showing a relationship between respective
fractions which flow out of a second-step fourth resin layer and
concentrations of respective amino acids based on the total amino
acids contained in an effluent;
[0020] FIG. 9 is a graph showing a relationship between respective
fractions of a valine-rich fraction which flows out of a third-step
third resin layer and concentrations of respective amino acids
based on the total amino acids contained in an effluent;
[0021] FIG. 10 is a graph showing a relationship between respective
fractions of a GABA-rich fraction which flows out of a third-step
third resin layer and concentrations of respective amino acids
based on the total amino acids contained in an effluent;
[0022] FIG. 11 is a schematic block diagram showing an apparatus
used in Example 7; and
[0023] FIG. 12 is a schematic block diagram showing an example of
an apparatus which can be used in recovering method 3-2-A.
DESCRIPTION OF REFERENCE NUMERALS
[0024] 1 to 8: First to eighth resin towers
[0025] F1: A supply cock for a raw material solution
[0026] F2-1, F2-2, F2-3, F2-4: Supply cocks for fractions C and D
of a second circulation system
[0027] E1 to E4: Supply cocks for eluent (1)
[0028] E5 to E8: Supply cocks for eluent (2)
[0029] R1: Cocks relating to a first circulation system
[0030] P1: A pump of the first circulation system
[0031] S1: A cock for taking out fractions C and D of the first
circulation system into a tank
[0032] S2: A cock for shutting off the first circulation system
[0033] R2: A cock relating to the second circulation system
[0034] P2: A pump of the second circulation system
[0035] A1 to A4: Cocks for recovering fraction A
[0036] B1 to B4: Cocks for recovering fraction B
[0037] C1 to C4: Cocks for recovering fraction C
[0038] D1 to D4: Cocks for recovering fraction D
DETAILED DESCRIPTION OF THE INVENTION
[0039] The mixed solutions used as raw materials in the method for
recovering amino acids according to the present invention include
CR waste liquor which is residues after recovery of effective
ingredients from molasses by CR treatment, resin waste liquor which
is regeneration waste liquor of ion exchange resins used for
purification of sugar liquid in the process of sugar manufacture,
yeast production waste liquor in bread manufacture, and alcoholic
fermentation waste liquor. Mixed solutions similar in composition
to these can be used as raw materials. Usually, these mixed
solutions have an rBx (refractometric Brix Degree; a solid
percentage measured by the refractive index) of 15 to 60, a cation
concentration of 0.5 to 3.0 N and an anion concentration of 0.4 to
2.8 N. Further, these mixed solutions contain 0 to 60 g of
saccharides, 1.0 to 2.0 g of the total amino acids, 0 to 30 g of
betaines, and a certain amount of coloring matters, per 100 g of
solid matter.
[0040] In the amino acids contained in sugar beets, usually, the
acidic amino acids include aspartic acid and glutamic acid, the
neutral amino acids include threonine, serine, glycine, alanine,
valine, leucine, isoleucine, methionine and .gamma.-amino butyric
acid (GABA), the aromatic amino acids include tyrosine and
phenylalanine, and the basic amino acids include histidine, lysine
and arginine. Accordingly, when the CR waste liquor is used as the
mixed solution comprising inorganic acid salts, coloring matters,
ashes, betaines, amino acids and non-electrolytes including
saccharides, the above-mentioned neutral amino acids, particularly
valine, leucine, isoleucine and GABA, and the aromatic amino acids,
particularly tyrosine, can be recovered according to the present
invention.
[0041] The resin layer comprising the Na type or K type IER, the
resin layer comprising the NH.sub.4 type IER, the resin layer
comprising the Ca type IER, and the resin layer comprising the Mg
type IER are hereinafter referred to as a first resin layer, a
second resin layer, a third resin layer and a fourth resin layer,
respectively.
[0042] As the resins used for the first resin layer (Na type or K
type IER) of the present invention, there are employed resins which
allow neutral amino acids to be well separable from the other
ingredients (such as ashes, coloring matters, betaines and acidic
amino acids). As the strongly acidic ion exchange resins used for
the third resin layer (Ca type IER) and the fourth resin layer (Mg
type IER), there are employed resins having good separability for
individual neutral amino acids. Thus, resins depending on the amino
acids to be recovered are suitably selected. As these resins, there
are usually used strongly acidic ion exchange resins in which
polystyrene resins crosslinked with divinylbenzene are sulfonated.
The degree of crosslinking is from 3% to 10%, and preferably from
5% to 8%. It is preferred that the ion exchange resins used for the
first, third and fourth resin layers of the present invention have
a uniform particle size for improving the separation performance.
Although the particle size ranges from 210 to 450 .mu.m, it varies
depending on the amino acid to be recovered and the maker of the CR
resin. Further, one of the conditions for selecting the resins is
physical durability.
[0043] The resins used in the present invention include, for
example, Amberlite CG6000, CR1310Na (manufactured by ORGANO
CORPORATION), Dowex chromatographic separation resin 99K-320,
XFS-43279 (manufactured by Dow Chemical Japan Limited) and DIAION
UBK530 (manufactured by MITSUBISHI CHEMICAL CORPORATION).
[0044] These resins can be substituted by other alkali metal type
strongly acidic ion exchange resins. However, the effect of
substitution is little from the economical viewpoint.
[0045] Strongly acidic ion exchange resins comprising sulfone
group-containing polystyrene crosslinked in a degree of 7% to 10%
by divinylbenzene are generally used for the NH.sub.4 type IER of
the second resin layer of the present invention. For example, Dowex
HCR-W2 (manufactured by Dow Chemical Japan Limited) and DIAION SK1B
(manufactured by MITSUBISHI CHEMICAL CORPORATION) are used. In this
second resin layer, the adsorption-fixed bed system is usually
employed.
[0046] The operation system of the first, third and fourth resin
layers may be any of the fixed bed system, the simulated moving bed
system and a combination thereof. In particular, a combination of a
new JO (multiple ingredient separation) system of ORGANO
CORPORATION or a new MCI (three ingredient separation) system of
MITSUBISHI CHEMICAL CORPORATION with the general simulated moving
bed system is preferred as a system which can efficiently separate
multiple ingredients of amino acids. The above-mentioned new JO
system is described in U.S. Pat. No. 5,198,120, and the
above-mentioned new MCI system is described in Japanese Patent
Laid-Open Publication (Hei) 7-232003.
[0047] The operating temperature of the first, third and fourth
resin layers of the present invention is preferably from 60 to
90.degree. C., and more preferably about 80.degree. C. Less than
60.degree. C. causes the problem of pollution caused by
microorganisms, whereas exceeding 90.degree. C. results in
increased deterioration of the resins.
[0048] Further, for the operating temperature of the second resin
layer of the present invention, solution passage and regeneration
are both performed at room temperature.
[0049] Recovering Method 1
[0050] A recovering method using the first resin layer (Na type or
K type IER) as the first-step resin layer and the second resin
layer (NH.sub.4 type IER) as the second-step resin layer will be
described as recovering method 1.
[0051] In the Na type or K type IER of the first resin layer,
inorganic salts and acidic materials are first eluted without being
adsorbed, due to the repulsion of cation in the solution for sodium
ions or potassium ions adsorbed in the resin, and no adsorption of
anion with resins. As a result, the pH of an effluent increases
after elution of inorganic salts and acidic materials.
[0052] Although water or an aqueous solution of a caustic alkali is
used as an eluent from the above-mentioned first resin layer, an
aqueous solution of sodium hydroxide having a pH of 8.5 to 11,
preferably 9.5 to 10.5, is usually used. When this eluent is used,
(1) coloring matters, (2) acidic amino acids, (3) ashes, (4)
neutral amino acids and saccharides and (5) betaines usually flow
out in this order. As a result, the first fraction in the effluent
mainly contains coloring matters, acidic amino acids and ashes, the
second fraction mainly contains neutral amino acids and
saccharides, and the third fraction mainly contains betaines.
[0053] This invention will be illustrated with reference to FIGS. 1
to 12 in details below, but the following disclosure shows
preferred embodiments of the invention and is not intended to limit
the scope of the invention.
[0054] In FIGS. 1 to 10, the supply rate of the raw material
solution supplied to a first resin layer was 5.56% of the apparent
volume of the resin layer. In FIGS. 1 to 10, the amount of each
fraction is 8.01 ml (2.67% of the apparent volume of the resin
layer).
[0055] FIG. 1 shows a relationship between respective fractions and
concentrations of respective ingredients contained in the effluent,
which is obtained by supplying CR waste liquor to the first resin
layer. The effluent can be separated into three fractions: a first
fraction (fraction numbers 1 to 6), a second fraction (fraction
numbers 7 to 11) and a third fraction (fraction numbers 12 to
20).
[0056] FIG. 2 shows a relationship between respective fractions and
concentrations of respective amino acids contained in the effluent,
which is obtained by supplying CR waste liquor to the first resin
layer.
[0057] In recovering method 1, the effluent of the second fraction
mainly containing neutral amino acids and saccharides, which flows
out of the above-mentioned first resin layer, is supplied to the
second resin layer comprising the ammonium type strongly acidic ion
exchange resin. An aqueous solution of ammonia is applied to this
second resin layer as an eluent to elute and recover amino acids
mainly comprising neutral amino acids adsorbed by the resin layer.
The aqueous solution of ammonia used is preferably aqueous ammonia
having a concentration of 1 N to 2 N.
[0058] An effluent containing the neutral amino acids in this
eluent is concentrated and adjusted to pH 5.7, thus obtaining
crystallized tyrosine, an aromatic amino acid. The purity of
tyrosine thus obtained is usually from 90% to 100% by weight, and
the recovery thereof is usually from 30% to 60% by weight (based on
tyrosine contained in the raw material).
[0059] A filtrate from which tyrosine is separated by filtration is
decolorized, concentrated and crystallized or pulverized, which
allows neutral amino acids other than tyrosine (such as leucine,
isoleucine, valine, serine and GABA) to be recovered. The total
content of leucine, isoleucine and valine thus obtained is usually
from about 30% to about 50% by weight based on a mixture of the
neutral amino acids, and the recovery of the neutral amino acids is
usually from 60% to 70% by weight (based on the neutral amino acids
contained in the raw material).
[0060] Recovering Method 2
[0061] A recovering method using the first resin layer (Na type or
K type IER) as the first-step resin layer and the third resin layer
(Ca type IER) as the second-step resin layer will be described as
recovering method 2.
[0062] In recovering method 2, of the above-mentioned three
fractions obtained from the first resin layer, the effluent of the
second fraction is supplied to the third resin layer comprising the
Ca type IER, and elution is conducted using water as an eluent,
thereby obtaining desired amino acids.
[0063] In the Ca type IER of the third resin layer, the saccharides
are completely separated from the amino acids, and the amino acids
are further subdivided. The reason for this is considered to be as
follows. That is to say, the calcium type strongly acidic ion
exchange resin is poor in ion exclusion ability and shows poor
molecular sieve effect, but is excellent in ligand exchange
ability, so that the saccharides can be completely separated from
the neutral amino acids and the aromatic amino acids. Further, the
individual neutral amino acids can also be separated by means of
dividing the obtained effluent into different fractions each
containing different concentration peaks.
[0064] In general, different from using Na type IER, when the
content of salts is high in the raw material, inorganic salts and
acidic materials are hard to be eluted first from the Ca type IER
owing to Ca type IER's poor ion exclusion ability. Thus, the pH of
the solution in the resin layer hardly changes stepwise (such as
neutral first, then, low pH, and finally high pH), resulting in
instability of a change in charge of amino acids.
[0065] Further, when the concentration of cations other than
calcium is high, the type of resin varies to result in insufficient
separation of amino acids from saccharide or insufficient
separation into each amino acid.
[0066] However, the present invention brings no problem, because
salts and cations are previously removed in the first resin
layer.
[0067] In the above-mentioned third resin layer, water used as the
eluent includes pure water, distilled water and deionized water,
and preferred is boiled ion-exchanged water.
[0068] Of the fractions of the effluent from the first resin layer,
the second fraction is supplied to the third resin layer, and the
above-mentioned eluent is further allowed to flow therein to
fractionate an effluent of the third resin layer, thereby roughly
dividing the effluent into two fractions: a first fraction mainly
containing saccharides and a second fraction mainly containing
neutral amino acids.
[0069] FIG. 3 shows a relationship between the respective fractions
of the effluent obtained by supplying the second fraction of the
effluent from the first resin layer to the third resin layer and
concentrations of saccharides, amino acids and ashes contained in
the effluent. Further, FIG. 4 shows a relationship between the
respective fractions of the effluent from the third resin layer and
concentrations of the respective amino acids based on the total
amino acids contained in the effluent.
[0070] The neutral amino acid-containing fraction (the second
fraction: fraction numbers 17 to 37) separated from the
saccharide-containing fraction (the first fraction: fraction
numbers 2 to 16) is concentrated, and the pH thereof is adjusted to
obtain crystallized tyrosine. The purity of tyrosine thus obtained
is usually from 90% to 100% by weight, and the recovery thereof is
usually from 30% to 60% by weight (based on tyrosine contained in
the raw material).
[0071] A filtrate from which tyrosine is separated by filtration is
decolorized, concentrated and crystallized or pulverized, which
allows neutral amino acids other than tyrosine (such as leucine,
isoleucine, valine, serine and GABA) to be recovered. The total
content of leucine, isoleucine and valine thus obtained is usually
from about 45% to about 60% by weight based on a mixture of the
neutral amino acids, and the recovery of the neutral amino acids is
usually from 50% to 70% by weight (based on the neutral amino acids
contained in the raw material).
[0072] Recovering Method 2-2
[0073] The fraction shown in FIG. 4 may be further subdivided into
a first fraction (fraction numbers 13 to 19) containing
saccharides, amino acids and ashes, a second fraction (fraction
numbers 20 to 24) containing GABA, alanine and valine, a third
fraction (fraction numbers 25 to 31) containing serine and valine,
and a fourth fraction (fraction numbers 32 to 37) containing
leucine, isoleucine and tyrosine.
[0074] The above-mentioned third fraction may be combined with the
above-mentioned fourth fraction to a fraction (fraction numbers 25
to 37) containing serine, valine, leucine, isoleucine and
tyrosine.
[0075] The effluent of the above-mentioned second fraction is
decolorized, concentrated and crystallized or pulverized, which
allows a mixture of neutral amino acids containing GABA, alanine
and valine to be recovered.
[0076] The effluent of the above-mentioned third fraction is
decolorized, concentrated and crystallized or pulverized, which
allows a mixture of neutral amino acids containing serine and
valine to be recovered.
[0077] Further, the effluent of the above-mentioned fourth fraction
is concentrated, and the pH thereof is adjusted to obtain
crystallized tyrosine. Amixture of neutral amino acids containing
leucine and isoleucine is obtained from the filtrate.
[0078] Recovering Method 2-2-A
[0079] In recovering method 2-2-A, the second fraction or the third
fraction of the effluent from the third resin layer in the
above-mentioned recovering method 2-2 is further supplied to the
fourth resin layer (Mg type IER), and various amino acids are
recovered using water as an eluent in the same manner as with the
third resin layer.
[0080] The Mg type IER of the fourth resin layer has the effect
that the elution order of neutral amino acids is different from
that in the Ca type IER, so that the composition of recovered
fractions of amino acids can be changed.
[0081] For the purpose of recovering GABA, the effluent of the
second fraction (fraction numbers 20 to 24) in FIG. 4 is used as
the fractionated effluent obtained from the third resin layer of
the recovering method 2-2. The effluent within this range is a
GABA-, alanine- and valine-rich fraction.
[0082] FIG. 5 shows a relationship between the respective fractions
of the effluent obtained by supplying the effluent within the range
of fraction numbers 20 to 24 in FIG. 4 to the fourth resin layer
and concentrations of the respective amino acids based on the total
amino acids contained in the effluent.
[0083] The effluent of fraction numbers 22 to 28 of FIG. 5 can be
recovered and concentrated to obtain a concentrated solution or a
powdery solid of GABA. The purity of GABA thus obtained is usually
from about 80% to about 100% by weight, and the recovery thereof is
usually from 10% to 40% by weight (based on GABA contained in the
raw material).
[0084] Further, the effluent of fraction numbers 15 to 21 of FIG. 5
can be recovered and concentrated to obtain a concentrated solution
or a powdery solid of a mixture containing alanine, valine and
serine.
[0085] Furthermore, for the purpose of recovering valine, the
effluent (the third fraction; within the range of fraction numbers
25 to 31) in FIG. 4 is used as the fractionated effluent obtained
from the third resin layer of the recovering method 2-2. The
effluent within this range is a valine- and serine-rich
fraction.
[0086] FIG. 6 shows a relationship between the respective fractions
of the fraction obtained by supplying the effluent within the range
of fraction numbers 25 to 31 in FIG. 4 to the fourth resin layer
and concentrations of the respective amino acids based on the total
amino acids contained in the effluent.
[0087] The effluent of fraction numbers 19 to 21 of FIG. 6 can be
recovered and concentrated to obtain a concentrated solution or a
powdery solid of valine. The purity of valine thus obtained is
usually from about 40% to about 60% by weight, and the recovery
thereof is usually from 10% to 30% by weight (based on valine
contained in the raw material).
[0088] Further, the effluent of fraction numbers 15 to 18 of FIG. 6
can be recovered and concentrated to obtain a concentrated solution
or a powdery solid of serine.
[0089] Recovering Method 3
[0090] A recovering method using the first resin layer (Na type or
K type IER) as the first-step resin layer and the fourth resin
layer (Mg type IER) as the second-step resin layer will be
described as recovering method 3. In recovering method 3, the
effluent of the second fraction obtained from the first resin layer
is supplied to the fourth resin layer, and allowed to flow out
using water as an eluent, thereby roughly dividing the effluent
into two fractions: a first fraction (fraction numbers 3 to 14)
mainly containing saccharides and a second fraction (fraction
numbers 15 to 28) mainly containing neutral amino acids and
ashes.
[0091] FIG. 7 shows a relationship between the respective fractions
of the effluent obtained by supplying the effluent of the second
fraction allowed to flow out of the first resin layer to the fourth
resin layer and concentrations of saccharides, amino acids and
ashes contained in the effluent. Further, FIG. 8 shows a
relationship between the respective fractions of the effluent
eluted from the fourth resin layer and concentrations of the
respective amino acids contained in the effluent.
[0092] The fraction containing neutral amino acids separated from
saccharides (the second fraction: fraction numbers 15 to 28) is
concentrated, and the pH thereof is adjusted to obtain crystallized
tyrosine. The purity of tyrosine thus obtained is usually from 90%
to 100% by weight, and the recovery thereof is usually from 30% to
50% by weight (based on tyrosine contained in the raw
material).
[0093] A filtrate from which tyrosine is separated by filtration is
decolorized, concentrated and crystallized or pulverized, which
allows neutral amino acids other than tyrosine (such as leucine,
isoleucine, valine, serine and GABA) to be recovered. The total
content of leucine, isoleucine and valine thus obtained is usually
from about 40% to about 50% by weight based on the neutral amino
acids contained in the raw material, and the recovery of the
neutral amino acids is usually from 40% to 70% by weight (based on
the neutral amino acids contained in the raw material).
[0094] Recovering Method 3-2
[0095] The fraction shown in FIG. 7 may be further subdivided into
a first fraction (fraction numbers 1 to 14) containing saccharides,
amino acids and ashes, a second fraction (fraction numbers 15 to
17) containing serine, a third fraction (fraction numbers 18 to 21)
containing alanine and valine, and a fourth fraction (fraction
numbers 22 to 28) containing tyrosine, leucine, isoleucine and
GABA.
[0096] The above-mentioned second fraction may be combined with the
above-mentioned third fraction to a fraction containing serine,
alanine and valine. In that case, the neutral amino acid-containing
fraction is divided into two fractions: a fraction containing
serine, alanine and valine and a fraction containing tyrosine,
leucine and isoleucine.
[0097] The effluent of the above-mentioned second fraction is
decolorized, concentrated and crystallized or pulverized, which
allows a mixture of neutral amino acids containing serine to be
recovered.
[0098] The effluent of the above-mentioned third fraction is
decolorized, concentrated and crystallized or pulverized, which
allows a mixture of neutral amino acids containing alanine and
valine to be recovered.
[0099] Recovering Method 3-2-A
[0100] In recovering method 3-2-A, the third fraction or the fourth
fraction of the effluent from the fourth resin layer in the
above-mentioned recovering method 3 is further supplied to the
third resin layer (Ca type IER), and various amino acids are
recovered using water as an eluent.
[0101] For the purpose of recovering valine, the effluent of the
third fraction (fraction numbers 18 to 21) in FIG. 8 is used as the
fractionated effluent obtained from the fourth resin layer of the
recovering method 3-2. The effluent within this range is an
alanine- and valine-rich fraction. FIG. 9 shows a relationship
between the respective fractions of the effluent obtained by
supplying the effluent within the range of fractions 18 to 21 in
FIG. 8 to the third resin layer and concentrations of the
respective amino acids based on the total amino acids contained in
the effluent.
[0102] The effluent of fraction numbers 28 to 31 of FIG. 9 can be
recovered and concentrated to obtain a concentrated solution or a
powdery solid of valine. The purity of valine thus obtained is
usually from about 30% to about 60% by weight, and the recovery
thereof is usually from 10% to 40% by weight (based on valine
contained in the raw material).
[0103] Further, the effluent of fraction numbers 19 to 26 of FIG. 9
can be recovered and concentrated to obtain a concentrated solution
or a powdery solid of alanine.
[0104] For the purpose of recovering GABA, the effluent of the
fourth fraction (fraction numbers 22 to 28) in FIG. 8 is used as
the fractionated effluent obtained from the fourth resin layer of
the recovering method 3-2. The effluent within this range is a
tyrosine-, leucine-, isoleucine- and GABA-rich fraction. FIG. 10
shows a relationship between the respective fractions of the
effluent obtained by supplying the effluent within the range of
fractions 22 to 28 in FIG. 8 to the third resin layer and
concentrations of the respective amino acids based on the total
amino acids contained in the effluent.
[0105] The effluent of fraction numbers 20 to 27 of FIG. 10 can be
recovered and concentrated to obtain GABA. The purity of GABA thus
obtained is usually from about 80% to about 100% by weight, and the
recovery thereof is usually from 20% to 40% by weight (based on
GABA contained in the raw material).
[0106] Further, the effluent of fraction numbers 29 to 39 of FIG.
10 is recovered and concentrated, and the pH thereof is adjusted to
obtain crystallized tyrosine.
[0107] A filtrate from which tyrosine is separated by filtration is
decolorized, concentrated and crystallized or pulverized, which
allows neutral amino acids other than tyrosine (leucine and
isoleucine) to be recovered.
[0108] In the recovering method of the present invention, the
effluents supplied to the second to forth resin layers may be used
as such or after concentration. The resulting amino acid-containing
effluents can be concentrated, pH adjusted and recrystallized by
conventional methods to obtain highly concentrated amino acid
solutions or crystallized amino acids (solid or powdery).
[0109] In the present invention, for example, in the case of
recovering method 2, a separation system described in Example 7
given later is the new JO (multiple ingredient separation) system
for the first resin layer, and the simulated moving bed system for
the third resin layer. A combination thereof is suitable for
separation recovery of a mixture of neutral amino acids and
tyrosine.
[0110] Similarly, in the case of recovering method 2-2-A or 3-2-A,
the new JO (multiple ingredient separation) system can be applied
to three systems: the first-step first resin layer, the second-step
fourth or third resin layer, and the third-step fourth or third
resin layer. In that case, the application of the new JO system
thereto makes it possible to continuously separate desired amino
acids. When circulation systems of the first resin layer, the third
resin layer and the fourth resin layer are each constituted, the
amino acids are further subdivided, and the desired amino acids can
be recovered by separation. This is therefore suitable for the
industrial recovery of the individual amino acids.
[0111] One embodiment thereof will be illustrated with reference to
FIG. 12. First, second and third circulation systems are formed by
resin layers 1 to 4, resin layers 5 to 8 and resin layers 9 to 12,
respectively. A raw material solution is introduced into a first
resin layer (Na type or K type IER), and separated into three
fractions in the first circulation system. Two fractions of them
are discharged outside the first circulation system to recoverthem.
The remaining one fraction is introduced into the resin layer 5 of
the second circulation system, and further fractionated into three
fractions. Similarly to the first circulation system, two fractions
are discharged outside the second circulation system to recover
them. The remaining one fraction is introduced into the resin layer
9 of the third circulation system, and divided into three fractions
to recover the respective fractions. Thus, the separated amino
acids can be recovered.
[0112] The present invention has the constitution and function as
described above. It becomes therefore possible to recover the
neutral amino acids and aromatic amino acids extremely high in
market value from the solutions containing trace amounts of amino
acids in highly concentrated inorganic acid salts, or highly
concentrated non-electrolytes such as saccharides, for example, CR
waste liquor and resin waste liquor which have hitherto been
subjected to the activated sludge process and discarded, or only
condensed for utilization as organic fertilizer, in beet sugar
manufacturing factories. Accordingly, the present invention
contributes largely to the environmental protection and the
industrial development.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0113] This invention will be illustrated with reference to
examples in more details below, but the following disclosure shows
preferred embodiments of the invention and is not intended to limit
the scope of the invention. Parts and percentages used in the
examples are by weight, unless otherwise specified.
EXAMPLE 1
(Recovery of Second Fraction)
[0114] As a raw material, CR waste liquor ("CCR" manufactured by
NIPPON BEET SUGAR MFG. CO., LTD.) was used. This liquor had an rBx
of 25, a cation concentration of 1.06 N, an anion concentration of
0.91 N and a pH of 10.0, and contained 33.6 g of saccharides, 12.3
g of betaines and 4.8 g of the total amino acids, per 100 g of
solid matter. This raw material solution was supplied to a first
resin layer comprising 300 ml of an Na type IER ("Amberlite CG6000"
manufactured by ORGANO CORPORATION) at 80.degree. C. at a space
velocity of 0.6 ml/ml-min. The supply rate thereof was 5.56% of the
apparent volume of the resin layer. Then, an aqueous solution of
sodium hydroxide adjusted to pH 10.0 and heated to 80.degree. C.
was supplied as an eluent to the first resin layer. Changes in
concentrations of respective ingredients to respective fractions
collected for every 2.67% (8.01 ml) of the apparent volume of the
first resin layer are as shown in FIG. 1, and changes in
concentrations of respective amino acids are as shown in FIG.
2.
[0115] In FIG. 2, the term "neutral amino acids (1)" indicates the
total of valine, leucine and isoleucine, and the term "other
neutral amino acids" means the total of the other neutral amino
acids.
[0116] It is known from these figures that neutral amino acids (1)
excluding acidic amino acids, and main aromatic amino acids flow
out together with saccharides. It is also known from these figures
that neutral amino acids (1) and the aromatic amino acids are
collectively eluted in fraction numbers 7 to 11 (the range of
13.35% of the apparent volume of the resin layer). It is therefore
suitable for the separation of neutral amino acids (1) and the
aromatic amino acids to use this range as a second fraction. An
effluent of the second fraction contained 20 g of the total amino
acids and 72 g of saccharides, per 100 g of solid matter.
EXAMPLE 2
(Recovery of Second Fraction)
[0117] Elution was conducted in the same manner as with Example 1
with the exception that pure water and aqueous solutions of sodium
hydroxide adjusted to pH 8.5, pH 10.0 and pH 11.0, respectively,
were used as eluents for the Na type IER (Amberlite CG6000) to
which CR waste liquor was supplied. Changes in concentrations of
respective ingredients to respective fractions were examined. As a
result, when the pH of the eluents was within the range of 8.5 to
11, preferably 9.5 to 10.5, neutral amino acids (1) and the
aromatic amino acids were collectively eluted in fraction numbers 7
to 11, similarly to FIGS. 1 and 2. It was therefore confirmed that
the use of fractions within this range as a second fraction was
suitable for the separation of neutral amino acids (1) and the
aromatic amino acids.
EXAMPLE 3
(Recovery of Second Fraction)
[0118] Elution was conducted in the same manner as with Example 1
with the exception that the CR waste liquor having a pH of 10.0
used in Example 1 and the CR waste liquor adjusted to pH 7.5 and pH
8.5 with sulfuric acid were supplied as such to a first resin layer
comprising an Na type IER (Dowex monospher 109 manufactured by Dow
Chemical Japan Limited) individually. Then, with the same manner as
with Example 1, aqueous solutions of sodium hydroxide adjusted to
pH 10.0 and heated at 80.degree. C. were used as eluents. As a
result, with respect to the pH of the CR waste liquor, the
respective amino acids were eluted within a wider fraction range at
a lower pH within this range (pH 7.5 to 10.0), which improved the
separability of the respective amino acids. Accordingly, the
adjustment of the pH of the raw material solution to 7.5 also made
it possible to recover the amino acids subdivided for every
specific ones.
EXAMPLE 4
(Recovering Method 1; Recovery of Amino Acids)
[0119] The effluent of the second fraction obtained in Example 1
contained 20 g of the total amino acids and 72 g of saccharides,
per 100 g of solid matter. This second fraction was supplied to a
second resin layer comprising 200 ml of an NH.sub.4 type IER
("Dowex HCR-W2" manufactured by Dow Chemical Japan Limited) in an
amount of 80 times the apparent volume of the resin layer at room
temperature at a space velocity of 10 ml/ml.multidot.min., thereby
allowing the amino acids to be adsorbed. Then, a 1 N aqueous
solution of ammonia was introduced into the second resin layer in
an amount of 4 times the apparent volume of the resin layer at room
temperature at a space velocity of 10 ml/ml-min. to eliminate and
recover amino acids mainly comprising neutral amino acids. Such an
adsorption-elimination operation increased the purity of the
recovered neutral amino acids from 20% to 90%, and the
concentration of the neutral amino acids in the effluent from 0.07%
to 1.2%.
[0120] The above-mentioned recovered solution was concentrated in a
concentrating apparatus to {fraction (1/5)} by volume. As a result,
the content of neutral amino acids (1) was 40.3% of the total amino
acids. After further adjustment to pH 5.7 with hydrochloric acid,
the resulting solution was allowed to stand at room temperature for
12 hours to precipitate tyrosine, an aromatic amino acid, followed
by filtration through a membrane filter having an average pore size
of 0.45 .mu.m. As a result, the ratio of neutral amino acids (1) to
the total amino acids contained in the filtrate increased to 53.8%,
which enabled crystallization by further concentration. Further,
tyrosine could be recovered from the above-mentioned filter. The
purity of tyrosine recovered was 98% by weight, and the recovery
thereof was 46% (based on tyrosine contained in the raw
material).
[0121] A filtrate from which tyrosine was separated by filtration
was decolorized, concentrated and crystallized or pulverized, which
allowed leucine, isoleucine, valine, serine and GABA of neutral
amino acids other than tyrosine to be recovered. The total content
of leucine, isoleucine and valine thus obtained was 36% based on
the neutral amino acids, and the recovery of the neutral amino
acids was 65% (based on the neutral amino acids contained in the
raw material).
[0122] As described in Example 3, when the pH of the CR waste
liquor used as the raw material was up to 7.5, at a lower pH, the
respective amino acids were eluted within a wider fraction range,
which improved the separability of the respective amino acids. In
the above elution, the peaks of the aromatic amino acids such as
tyrosine and phenylalanine appeared considerably later than those
of the other amino acids. Accordingly, the aromatic amino acids can
also be separately recovered by adjusting the pH of the eluent.
Accordingly, the adjustment of the pH of the raw material solution
also made it possible to recover the amino acids subdivided for
every specific ones.
EXAMPLE 5
(Recovering Method 2; Recovery of Second Fraction)
[0123] The CR waste liquor was fractionated in the same manner as
with Example 1, and fraction numbers 1 to 6 (a solution
corresponding to 16.02% of the apparent volume of the resin layer)
flowing out after a solution corresponding to the volume of a pipe
installed behind the first resin layer was allowed to flow out was
taken as a first fraction, fraction numbers 7 to 11 (a solution
corresponding to 13.35% of the apparent volume of a resin layer
subsequent thereto) as a second fraction, and fraction numbers 12
to 20 (a solution corresponding to 24.03% of the apparent volume of
a resin layer subsequent thereto) as a third fraction. Of these,
only the second fraction was supplied to a third resin layer
comprising 300 ml of an Ca type IER ("Amberlite CG6000"
manufactured by ORGANO CORPORATION) at the same solution passage
temperature (80.degree. C.), space velocity and supply rate as a
solution allowed to flow out of the first resin layer.
EXAMPLE 6
(Recovering Method 2; Recovery of Amino Acids)
[0124] Boiled ion-exchanged water was supplied as an eluent
(80.degree. C.) to the third resin layer prepared in Example 5. The
composition of an effluent allowed to flow out of the third resin
layer was as shown in FIGS. 3 and 4 for each fraction number. FIG.
3 shows changes in composition of saccharides, amino acids and
ashes within the range of fraction numbers 2 to 40 of fraction
numbers 1 to 42 collected. Of these, fraction numbers 15 to 38 were
collected as an amino acid fraction. FIG. 4 shows changes in
composition of the respective amino acids within the range of
fraction numbers 17 to 37.
[0125] After the amino acid fraction obtained from the third resin
layer was concentrated to {fraction (1/6)} by volume, it was
adjusted to pH 5.7 with hydrochloric acid. The resulting solution
was allowed to stand at room temperature for 24 hours to separate
and recover crystallized tyrosine. The recovery of tyrosine was 45%
based on tyrosine contained in the raw material, and the purity
thereof was 98%. On the other hand, the separated solution was
decolorized with activated carbon, followed by concentration and
crystallization to obtain powdery neutral amino acids containing
leucine and isoleucine as main ingredients and valine, serine and
GABA as subsidiary ingredients. The recovery of the resulting
powdery neutral amino acids was 56% by weight in total (based on
the neutral amino acids contained in the CR waste liquor). Further,
the total content of leucine, isoleucine and valine contained in
the powdery neutral amino acids was 52% by weight.
EXAMPLE 7
(Recovering Method 2; Recovery of Second Fraction and Recovery of
Amino Acids)
[0126] As shown in FIG. 11, 8 resin towers having an inner diameter
of 108.3 mm and a resin layer height of 1,000 mm were arranged. The
first to fourth resin towers were filled with an Na type IER
("Amberlite CG6000" manufactured by ORGANO CORPORATION), and an
aqueous solution of sodium hydroxide (pH 10.0) was used as an
eluent (hereinafter referred to as "eluent (1)"), thereby forming a
first circulation system. The fifth to eighth resin towers were
filled with a Ca type IER ("Amberlite CG6000" manufactured by
ORGANO CORPORATION), and pure water was used as an eluent
(hereinafter referred to as "eluent (2)"), thereby forming a second
circulation system. Using the first to eighth resin towers,
recovering method 2 of the present invention was carried out at a
liquid temperature of 80.degree. C.
[0127] In the first circulation system, as a preparatory step, a
cock F1 was opened to supply 1.61 liters of CR waste liquor ("CCR"
manufactured by NIPPON BEET SUGAR MFG.CO., LTD., rBx: 60) as a raw
material solution to the third resin tower, and at the same time,
the same amount of a liquid in the first resin tower was allowed to
flow out through a cock A1. After the raw material solution was
introduced into the first circulation system, cocks S2 and R1 were
opened, and the all other cocks were closed to circulate the raw
material solution through the first to fourth resin towers already
filled with eluent (1) with a circulation pump P1, thereby forming
a state in which a first fraction (fraction A mainly comprising
ashes), a second fraction (a mixed fraction comprising fraction C
mainly containing saccharides and fraction D mainly containing
neutral amino acids) and a third fraction (fraction B mainly
comprising betaines) each formed separated patterns of the
fractions, and concentration peaks of the respective fractions were
separated.
[0128] As a first step, the cock F1, a cock E1, a cock A4 and a
cock S1 were opened, and the all other cocks including the cock S2
were closed in a stage in which the concentration peak of fraction
A was approximately shifted to the fourth resin tower, the
concentration peak of the mixed fraction of fraction C and fraction
D to the second resin tower, and the concentration peak of fraction
B to the first resin tower, while operating the circulation pump
P1. In this state (no circulation flow of towers 1 to 4 was
formed), 1.61 liters of the raw material solution was supplied to
the third resin tower through the cock F1, and 0.44 liters of
fraction A was recovered through the cock A4 at the bottom of the
first resin tower. At the same time, 3.90 liters of eluent (1) was
supplied to the first resin tower through the cock E1, and 5.06
liters of the mixed fraction of fraction C and fraction D was taken
out of the bottom of the second resin tower and once placed in a
tank T.
[0129] As a second step, the cock R1, a cock E2, a cock B2, the
cock S2 and the cock A1 were opened, and the all other cocks of the
first circulation system were closed. Eluent (1) was supplied to
the second resin tower through the cock E2, fraction B was
recovered through the cock B2 at the bottom of the second resin
tower, and fraction A was further recovered through the cock A1 at
the bottom of the first resin tower, while forming a circulation
flow in the first to fourth resin towers.
[0130] Then, as a third step, the cock R1, a cock E3, a cock B3,
the cock S2 and a cock A2 were opened, and the all other cocks of
the first circulation system were closed. Eluent (1) was supplied
to the third resin tower through the cock E3, fraction B was
recovered through the cock B3 at the bottom of the third resin
tower, and fraction A was recovered through the cock A2 at the
bottom of the second resin tower, while forming a circulation flow
in the first to fourth resin towers.
[0131] Further, as a fourth step, the cock R1, a cock E4, a cock
B4, the cock S2 and a cock A3 were opened, and the all other cocks
of the first circulation system were closed. Eluent (1) was
supplied to the fourth resin tower through the cock E4, fraction B
was recovered through the cock B4 at the bottom of the fourth resin
tower, and fraction A was further recovered through the cock A3 at
the bottom of the third resin tower, while forming a circulation
flow in the first to fourth resin towers.
[0132] Thus, in the second to fourth steps, 2.18 liters of eluent
(1) was supplied through each of the cocks E2, E3 and E4, 0.61
liters of fraction A was recovered through each of the cocks A1, A2
and A3, and 1.57 liters of fraction B was recovered through each of
the cocks B2, B3 and B4.
[0133] According to the above-mentioned first to fourth steps in
the first circulation system, the mixed fraction of fraction C and
fraction D was once recovered in the tank T, and then, concentrated
to about {fraction (1/2)} by volume. In the present invention, the
recovered mixed fraction of fraction C and fraction D may be used
as such without concentration. Then, the mixed concentrated
fraction was divided into a part for the preparatory step and a
part for the subsequent steps. And the each part of the mixed
concentrated fraction was introduced into the second circulation
system in the manner described as follows. In the preparatory step,
the filled solution in the second circulation system was taken out
in an amount corresponding to that of the solution introduced.
[0134] Further, fraction A and fraction B could be recovered from
the first circulation system.
[0135] The operating temperature of the first circulation system
was 80.degree. C.
[0136] In the second circulation system, as a preparatory step, the
mixed fraction of fraction C and fraction D of the first
circulation system, which was stored in the tank T, was partly
introduced into the fifth resin tower of the second circulation
system. A cock R2 was opened, the all other cocks including a cock
S2 were closed, and a circulation flow was formed in the fifth to
eighth resin towers while operating a circulation pump P2, thereby
forming a state in which concentration peaks of fraction C mainly
comprising saccharides and fraction D mainly comprising neutral
amino acids were separated in the fifth resin tower and the seventh
resin tower, respectively. The remainder of the mixed fraction in
the tank T was divided into four equal parts, which were supplied
to the fifth to eighth resin towers, respectively. The subsequent
and later steps of the second circulation system required no
separation of concentration peaks by circulating an introduced
solution in the resin towers, because the concentration peaks were
already separated in the preparatory step.
[0137] As a first step of the second circulation system, the cock
R2, a cock E5, a cock C1 and a cock D3 were opened, and the all
other cocks were closed. The mixed solution of fraction C and
fraction D was introduced into the seventh resin tower through a
cock F2-3, while forming a circulation flow in the fifth to eighth
resin towers. At the same time, eluent (2) was supplied to the
fifth resin tower through the cock E5. Thus, fraction C was
recovered through the cock C1 at the bottom of the fifth resin
tower, and fraction D was recovered through the cock D3 at the
bottom of the seventh resin tower.
[0138] Then, as a second step, the cock R2, a cock E6, a cock C2
and a cock D4 were opened, and the all other cocks were closed. The
mixed solution of fraction C and fraction D was introduced into the
eighth resin tower through a cock F2-4, while forming a circulation
flow in the fifth to eighth resin towers. At the same time, eluent
(2) was supplied to the sixth resin tower through the cock E6.
Thus, fraction C was recovered through the cock C2 at the bottom of
the sixth resin tower, and fraction D was recovered through the
cock D4 at the bottom of the eighth resin tower.
[0139] Subsequently, as a third step, the cock R2, a cock E7, a
cock C3 and a cock D1 were opened, and the all other cocks were
closed. The mixed solution of fraction C and fraction D was
introduced into the fifth resin tower through a cock F2-1, while
forming a circulation flow in the fifth to eighth resin towers. At
the same time, eluent (2) was supplied to the seventh resin tower
through the cock E7. Thus, fraction C was recovered through the
cock C3 at the bottom of the seventh resin tower, and fraction D
was recovered through the cock D1 at the bottom of the fifth resin
tower.
[0140] Further, as a fourth step, the cock R2, a cock E8, a cock C4
and a cock D2 were opened, and the all other cocks were closed. The
mixed solution of fraction C and fraction D was introduced into the
sixth resin tower through a cock F2-2, while forming a circulation
flow in the fifth to eighth resin towers. At the same time, eluent
(2) was supplied to the eighth resin tower through the cock E8.
Thus, fraction C was recovered through the cock C4 at the bottom of
the eighth resin tower, and fraction D was recovered through the
cock D2 at the bottom of the sixth resin tower. The first to fourth
steps were hereafter repeated to conduct continuous operation. In a
cycle having no preparatory step, the mixed solution of fraction C
and fraction D was divided into four equal parts Like this, in the
second cycle and later, 0.71 liters of the mixed solution of
fraction C and fraction D was recovered through each of the cocks
F2-1, F2-2, F2-3 and F2-4, 3.49 liters of eluent (2) was supplied
through each of the cocks E5, E6, E7 and E8, 0.84 liters of
fraction C was recovered through each of the cocks C1, C2, C3 and
C4, and 3.36 liters of fraction D was recovered through each of the
cocks D3, D4, D1 and D2.
[0141] The operating temperature of the second circulation system
was 80.degree. C.
[0142] In this way, fraction C and fraction D could be separated
from each other and recovered by repeating the preparatory step and
the first to fourth steps of the second circulation system, in
parallel with the respective steps of the first circulation system.
Crystallized tyrosine was separated and recovered from the
resulting fraction D in the same manner as with Example 1. The
recovery of tyrosine was 48%, and the purity thereof was 98%.
Powdery neutral amino acids containing leucine and isoleucine as
main ingredients and valine, serine and GABA as subsidiary
ingredients could be obtained. The recovery of the resulting
powdery neutral amino acids from the CR waste liquor was 60% in
total. Further, the total content of leucine, isoleucine and valine
contained in the powdery neutral amino acids was 53%.
EXAMPLE 8
(Recovering Method 2-2-A; Recovery of GABA)
[0143] In the same manner as with Example 6, boiled ion-exchanged
water was supplied as an eluent to the third resin layer prepared
in Example 5, and fraction numbers 20 to 25 were collected as an
amino acid fraction (GABA-rich fraction). The purity of GABA in
this GABA-rich fraction was 80%. The above-mentioned GABA-rich
fraction was supplied to a fourth resin layer comprising 300 ml of
an Mg type IER (DIAION UBKS30 manufactured by MITSUBISHI CHEMICAL
CORPORATION) at the same solution passage temperature (80.degree.
C.), space velocity (0.6 ml/ml.multidot.min.) and supply rate
(5.56% per resin volume) as a solution allowed to flow out of the
first resin layer.
[0144] The composition of the GABA-rich fraction allowed to flow
out of the fourth resin layer is as shown in FIG. 5 for each
fraction number. The effluent of fraction numbers 22 to 28 of FIG.
5 was recovered and concentrated to separate and recover GABA. The
recovery of GABA was 30% (based on GABA contained in the raw
material), and the purity thereof was 88%.
EXAMPLE 9
(Recovering Method 2-2-A; Recovery of Valine)
[0145] In the same manner as with Example 8, boiled ion-exchanged
water was supplied as an eluent (80.degree. C.) to the third resin
layer prepared in Example 5, and fraction numbers 28 to 30 were
collected as an amino acid fraction (valine-rich fraction). The
purity of valine in this valine-rich fraction was about 30%. The
above-mentioned valine-rich fraction was supplied to the fourth
resin layer in the same manner as with Example 9.
[0146] The composition of the valine-rich fraction allowed to flow
out of the fourth resin layer was as shown in FIG. 6 for each
fraction number. The effluent of fraction numbers 19 to 21 of FIG.
6 was recovered and concentrated to separate and recover valine.
The recovery of valine was 15% (based on valine contained in the
raw material), and the purity thereof was 50%.
EXAMPLE 10
(Recovering Method 3; Recovery of Second Fraction and Recovery of
Amino Acids)
[0147] In the same manner as with Example 5, the CR waste liquor
was fractionated, and the second fraction was supplied to the
fourth resin layer comprising 300 ml of the Mg type IER (DIAION
UBK530 manufactured by MITSUBISHI CHEMICAL CORPORATION) at the same
solution passage temperature, space velocity and supply rate as a
solution allowed to flow out of the first resin layer.
[0148] Boiled ion-exchanged water was supplied as an eluent
(80.degree. C.) to the above-mentioned fourth resin layer. The
composition of an effluent allowed to flow out of the fourth resin
layer was as shown in FIGS. 7 and 8 for each fraction number. FIG.
7 shows changes in composition of saccharides, amino acids and
ashes within the range of fraction numbers 2 to 40 of fraction
numbers 1 to 42 collected. Of these, fraction numbers 14 to 31 were
collected as an amino acid fraction. FIG. 8 shows changes in
composition of the respective amino acids within the range of
fraction numbers 14 to 31.
[0149] After the amino acid fraction obtained from the fourth resin
layer was concentrated to {fraction (1/6)} by volume, it was
adjusted to pH 5.7 with hydrochloric acid. The resulting solution
was allowed to stand at room temperature for 24 hours to separate
and recover crystallized tyrosine. The recovery of tyrosine was 42%
(based on tyrosine contained in the raw material), and the purity
thereof was 95%. On the other hand, the separated solution was
decolorized with activated carbon, followed by concentration and
crystallization to obtain powdery neutral amino acids containing
leucine and isoleucine as main ingredients and valine, serine and
GABA as subsidiary ingredients. The recovery of the resulting
powdery neutral amino acids from the CR waste liquor was 50% (based
on the neutral amino acids contained in the raw material). Further,
the total content of leucine, isoleucine and valine contained in
the powdery neutral amino acids was 36%.
EXAMPLE 11
(Recovering Method 3-2-A; Recovery of GABA)
[0150] In the same manner as with Example 10, the CR waste liquor
was fractionated, and the second fraction was supplied to the
fourth resin layer. Boiled ion-exchanged water was supplied as an
eluent (80.degree. C.) to the fourth resin layer, and fraction
numbers 22 to 32 were collected as an amino acid fraction
(GABA-rich fraction).
[0151] The composition of the GABA-rich fraction allowed to flow
out of the third resin layer was as shown in FIG. 9 for each
fraction number. The effluent of fraction numbers 20 to 27 of FIG.
9 was recovered and concentrated to separate and recover GABA. The
recovery of GABA was 31% (based on GABA contained in the raw
material), and the purity thereof was 90%.
EXAMPLE 12
(Recovering Method 3-2-A; Recovery of Valine)
[0152] In the same manner as with Example 10, the CR waste liquor
was fractionated, and the second fraction was supplied to the
fourth resin layer. Boiled ion-exchanged water was supplied as an
eluent (80.degree. C.) to the fourth resin layer, and fraction
numbers 18 to 20 were collected as an amino acid fraction
(valine-rich fraction). The purity of valine in this valine-rich
fraction was about 30%. The above-mentioned valine-rich fraction
was supplied to the fourth resin layer in the same manner as with
Example 11. The composition of the valine-rich fraction allowed to
flow out of the fourth resin layer was as shown in FIG. 10 for each
fraction number. The effluent of fraction numbers 28 to 31 of FIG.
10 was recovered and concentrated to separate and recover valine.
The recovery of valine was 25% (based on the neutral amino acids
contained in the raw material), and the purity thereof was 50%.
* * * * *