JP3437103B2 - How to regenerate seasoning liquid after pickling - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for regenerating a seasoning solution after being dipped by an electrodialysis method for desalting and deoxidizing.

[0002]

2. Description of the Related Art Among pickles such as plum pickled products, there are seasoned pickles seasoned with various pickled seasonings. For example, a pickled plum product is produced by salting and pickling ume and then dipping it in a pickle seasoning liquid for pickling plum. The seasoning liquid is a mixture of amino acids, saccharides, salt, citric acid, alcohol and the like. The pickled seasoning liquid remaining after the pickled plums are taken out is referred to as a post-pickling seasoning liquid in this specification.

Since the salt and citric acid in the seasoning liquid after pickling are increased, more than half of the seasoning liquid after pickling is discarded, and the newly prepared pickling seasoning liquid is mixed and reused. Has been. However, this method is uneconomical because a large amount of expensive pickled seasoning liquid is discarded, and the disposal cost of the waste liquid as an environmental measure is large.

Recently, an attempt has been made to desalt the seasoning liquid after pickling by electrodialysis. In this case, since the salt is preferentially desalted and the citric acid is hardly removed due to the usual electrodialysis method, it is the actual situation that the seasoning liquid cannot be efficiently collected after the pickling. Even in the usual electrodialysis method, the removal rate of citric acid can be increased to 30% or more by continuing to energize even after salt is almost 100% desalted. However, this method has drawbacks such that it is easily spoiled because most of the salt is removed, and the loss of other valuable components increases.

[0005]

DISCLOSURE OF THE INVENTION The present invention aims to suppress loss of active ingredients (amino acids, sugars, etc.) in seasoning liquid after pickling as much as possible, and salt such as salt brought in from the previous step of pickling and pickled food. The purpose of the present invention is to make a composition suitable for reuse by desalting and deoxidizing an organic acid such as citric acid which is eluted from the soup after seasoning in a well-balanced manner.

[0006]

According to the present invention, a plurality of cation exchange membranes and anion exchange membranes are alternately arranged between an anode and a cathode, and the cathode side is partitioned by the cation exchange membranes. A desalting chamber having an anode side partitioned with an anion exchange membrane, and a concentrating chamber having an anode side partitioned with a cation exchange membrane and a cathode side partitioned with an anion exchange membrane. The salt solution and the organic acid are removed from the seasoning solution after being dipped in the anion-exchange membrane by supplying the seasoning solution after dipping into But film thickness 1-150
μm, ion exchange capacity 0.5-4 meq / g-dry resin, fixed ion concentration 1-10 meq / g-H ₂ O, 0.
A strongly basic anion exchange membrane having an electric resistance value of 0.1 to 0.9 Ω · cm ² in a 5 eq / L sodium chloride aqueous solution, and desalting by adding an alkali to the electrolyte solution in the concentrating chamber. Provided is a method for regenerating a seasoning liquid after pickling, which is characterized by operating while neutralizing an organic acid that has permeated from a room.

In the present invention, the salts are inorganic salts such as sodium chloride, and the organic acids are citric acid and the like.
As an example of pickled seasoning liquid suitable for the treatment according to the present invention,
Table 1 shows a component table. The pickled seasoning liquid contains sodium chloride, citric acid, sugar, amino acids and the like. In Table 1, the new seasoning liquid means a newly prepared seasoning liquid, and the seasoning liquid after soaking is the seasoning liquid after the material is dipped and the material is taken out. In the seasoning liquid after pickling, sodium chloride is brought in from the previous step of pickling, and citric acid is eluted from the pickling, so that it increases respectively. This composition table shows an example, and the present invention is not limited to the values in this composition table. In the present specification, L, which is a unit of capacity, is represented by L.

[0008]

[Table 1]

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a plurality of cation exchange membranes and anion exchange membranes are alternately arranged between an anode and a cathode, and the cathode side is partitioned by the cation exchange membranes. An electrodialysis tank having a desalting chamber whose side is partitioned by an anion exchange membrane, and a concentrating chamber whose anode side is partitioned by a cation exchange membrane and whose cathode side is partitioned by an anion exchange membrane is used, and the desalting chamber is described above. After pickling, the seasoning liquid is supplied and processed.
When the seasoning liquid after pickling was supplied to the desalting chamber of the electrodialysis tank to remove sodium chloride and citric acid, the inventor investigated the behavior in detail and confirmed the following.

That is, as the strongly basic anion exchange membrane, for example, the membrane thickness is 80 to 200 μm, the ion exchange capacity is 3 to 3.5 meq / g-dry resin, and the fixed ion concentration is 6 to 8 meq / g-H _2. O, electric resistance value in a 0.5 eq / L sodium chloride aqueous solution is 1.0 to 4.0 Ω · c
When an anion exchange membrane of m ² is used, most of the substances removed from the seasoning liquid after dipping in the desalting chamber (hereinafter referred to as desalting liquid) are sodium chloride, which is a strong electrolyte, The weak electrolyte, citric acid, has a deoxidation rate of about several percent.
Then, after the removal of sodium chloride is almost completed, the removal of citric acid proceeds.

In the case of the composition table of Table 1, the required removal rate of citric acid is about 35%, but when the above-mentioned anion exchange membrane is used, sodium chloride is added to achieve this removal rate of citric acid. Almost 100% must be removed, and sodium chloride required as a seasoning solution is also removed. The reason why sodium chloride and citric acid are removed in this order is considered to be due to the following mechanism.

From the early stage to the middle stage of operation when sodium chloride is sufficiently present in the liquid in the desalting chamber, most of the electric current is due to electrophoresis of sodium chloride which is a strong electrolyte. At this point, citric acid is also removed by several%, but this contributes largely to migration by migration through the anion exchange membrane in addition to electrophoresis. When the removal of sodium chloride progresses and the amount of sodium chloride in the liquid in the desalting chamber decreases, citric acid plays a role of carrying current, and electrophoresis mainly plays a role in the removal of citric acid. .

In the present invention, the anion exchange membrane has a film thickness of 1 to 150 μm and an ion exchange capacity of 0.5 to 4 meq / g.
- dry resin, a fixed ion concentration 1~10meq / g-H ₂
It is necessary that the strong basic anion exchange membrane has an electric resistance value of 0.1 to 0.9 Ω · cm ² in an aqueous solution of O and 0.5 eq / L of sodium chloride. Since this anion exchange membrane is an anion exchange membrane having a low electric resistance, it is possible to suppress the electrophoresis of sodium chloride and promote the movement of citric acid.

It is more preferable that the anion exchange membrane has a thickness of 5 to 25 μm. Ion exchange capacity is 0.8 ~
More preferably, it is 2.0 meq / g-dry resin. More preferably, the fixed ion concentration is ₂ to 5 meq / g-H2O. The electric resistance value in a 0.5 eq / L sodium chloride aqueous solution is 0.2 to 0.5 Ω · cm ^2.
Is more preferable.

In the present invention, it is necessary to add an alkali to the electrolyte solution in the concentrating chamber (hereinafter referred to as the concentrating liquid) to neutralize the organic acid that has permeated from the desalting chamber. The pH of the concentrated solution is preferably adjusted to 4-10. It is more preferable to adjust the pH of the concentrated solution to 6-8. The addition of alkali is suitable for adjusting the pH of the concentrated solution. The alkali to be added is not particularly limited, but sodium hydroxide or potassium hydroxide is preferably used.

FIG. 1 shows an example of an apparatus for implementing the present invention. The electrodialysis tank 15 has an anode chamber 13 in which an anode is arranged and a cathode chamber 14 in which a cathode is arranged. The electrode liquid is supplied from the electrode liquid tank 12 to the anode chamber and the cathode chamber.
Electric current is supplied to the anode and the cathode from a power source (not shown). A plurality of cation exchange membranes and anion exchange membranes are alternately arranged between the anode chamber 13 and the cathode chamber 14 to form a desalting chamber 4 and a concentrating chamber 9. In FIG. Are simplified.

In this apparatus, continuous operation is possible, but the batch operation will be described below as an example. After the pickling, the seasoning liquid 1 is filtered by the filtering device 2, and then the desalting liquid tank 3
Supply a predetermined amount to. Concentrated liquid tank 8 and electrode liquid tank 12
Then, a predetermined liquid is charged therein, the valve 6 is closed, the valve 7 is opened, and the liquid is supplied to the electrodialysis tank 15 for circulation. After adjusting the circulation amount to a predetermined value, energization is started.

The pH of the concentrated solution was measured with a pH meter 10 to
The sodium hydroxide solution 11 is supplied by a metering pump or the like so that the value becomes 6 to 8. The end of energization is determined by the conductivity of the desalination solution. When the electric conductivity meter 5 of the desalted solution is below a predetermined value, the valve 6 is opened and the valve 7 is closed to transfer the desalted solution to another tank. When the transfer of the desalted solution is completed, the operation returns to the beginning and the next batch operation starts. In addition, this description shows the basic operation procedure, and the actual operation is
It can be almost automated unmanned driving.

FIG. 2 shows the arrangement of ion exchange membranes in the electrodialysis tank 15. That is, in the electrodialysis tank 15, the cation exchange membrane K and the anion exchange membrane A are provided between the anode and the cathode.
And a plurality of sheets are alternately arranged, and a desalting chamber D and a concentrating chamber C are provided.
Are formed alternately.

[0020]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples.

[Example 1] A strongly acidic cation exchange membrane (Serumion CMV, manufactured by Asahi Glass Co., Ltd.) having an electric resistance of 3 Ω · cm ² and a film thickness of 110 μm as a cation exchange membrane, and a membrane as an anion exchange membrane. Strongly basic anion exchange membrane (Asahi Glass) having a thickness of 15 μm, an ion exchange capacity of 1.2 meq / g-dry resin, and an electric resistance value of 0.3 Ω · cm ² in a 0.5 eq / L sodium chloride aqueous solution. Effective membrane area of 0.21m ² combined with Selemion APS manufactured by the company
Using an electrodialysis tank (0.021 m ² / pair × 10 pairs), 5 L of the seasoning liquid was treated after being dipped. Sodium hydroxide was added to the concentrate to adjust the pH to 6-8. Table 2 shows these conditions. In Table 2, voltage is the voltage between the anode and cathode.

[0022]

[Table 2]

Table 3 shows the results of measuring the liquid amount, pH, NaCl concentration and citric acid concentration of the desalted solution.

[0024]

[Table 3]

Table 4 shows the removal rates of sodium chloride and citric acid. When the sodium chloride removal rate was about 63%, the target citric acid removal rate of 35% was almost achieved.

[0026]

[Table 4]

Example 2 (Comparative Example) The same cation exchange membrane as in Example 1 was used, and the thickness of the anion exchange membrane was 110 μm.
m, an ion exchange capacity of 3.5 meq / g-dry resin,
An effective membrane area in combination with a strongly basic anion exchange membrane (trade name: Selemion AMV, manufactured by Asahi Glass Co., Ltd.) having an electric resistance of 2.5 Ω · cm ² in a 0.5 eq / L sodium chloride aqueous solution. 21m ² (0.021m ² / pair × 1
0 pair) of electrodialyzer was used to treat 5 L of seasoning liquid after soaking. The pH of the concentrate was left unadjusted. Table 5 shows these conditions. In Table 5, the voltage is the voltage between the anode and the cathode.

[0028]

[Table 5]

Table 6 shows the results of measuring the liquid amount, pH, NaCl concentration and citric acid concentration of the desalted solution.

[0030]

[Table 6]

Table 7 shows the removal rates of sodium chloride and citric acid. The target removal rate of citric acid of 35% could not be achieved unless the removal rate of sodium chloride was 99% or more.

[0032]

[Table 7]

[0033]

INDUSTRIAL APPLICABILITY The present invention uses an anion exchange membrane having a low ion exchange capacity and a low electric resistance, and performs electrodialysis while neutralizing the concentrated solution, whereby the seasoning solution after pickling can be efficiently regenerated, Not only does it have an economic advantage, but it also has excellent effects on the environment.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing an example of an apparatus for carrying out the present invention.

FIG. 2 is a view showing the arrangement of ion exchange membranes in the electrodialysis tank of FIG.

[Explanation of symbols]

1: Seasoning liquid after pickling 2: Filtration device 3: Desalination tank 4: Desalination chamber 5: Conductivity meter 6: Valve (delivery of desalination solution) 7: Valve (circulation of desalination solution) 8: Concentrated liquid tank 9: Concentration room 10: pH meter 11: Sodium hydroxide solution for neutralization 12: Electrode solution tank 13: Anode chamber 14: Cathode chamber 15: Electrodialysis tank K: Cation exchange membrane A: Anion exchange membrane D: Desalination chamber C: Concentration chamber

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor ▲ Taka ▼ Yutaka Kurata 3-4-1, Seta, Otsu City, Shiga Prefecture, Takara Shuzo Co., Ltd., Central Research Laboratory (72) Inventor Tatsuya Kawabe, 3 Seta, Otsu City, Shiga Prefecture No. 4-1 Sake Brewing Co., Ltd. Central Research Laboratory (72) Inventor Hideo Morita 3-4-1, Seta, Otsu City, Shiga Prefecture Ryushu Brewing Co., Ltd. Central Research Laboratory (56) Reference JP-A-7-67526 ( JP, A) JP-A 2-115025 (JP, A) JP-A 1-284308 (JP, A) JP-B 57-24103 (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) A23B 7/00-9/34 B01D 53 / 22,61 / 00-71/82 C02F 1/44 JISST file (JOIS)

Claims (2)

(57) [Claims] 1. A plurality of cation exchange membranes and anion exchange membranes are alternately arranged between an anode and a cathode, wherein the cathode side is partitioned by the cation exchange membranes and the anode side is the anion exchange membranes. Using an electrodialysis tank that has a compartmentalized demineralization chamber and a concentrating chamber in which the anode side is partitioned by a cation exchange membrane and the cathode side is partitioned by an anion exchange membrane, the seasoning liquid is supplied after being immersed in the desalination chamber. Then, by supplying an electrolyte solution to the concentrating chamber and energizing it to remove salts and organic acids from the seasoning solution after pickling and reusing the solution, the anion exchange membrane has a thickness of 1 to 150 μm, Ion exchange capacity 0.5-4 meq / g-dry resin, fixed ion concentration 1
~10meq / g-H ₂ O, the electrical resistance value in an aqueous sodium chloride solution 0.5eq / L 0.1~0.9Ω · cm
² is a strongly basic anion exchange membrane and is operated by neutralizing the organic acid that has permeated from the desalting chamber by adding an alkali to the electrolyte solution in the concentrating chamber. How to regenerate seasoning liquid. 2. The method for regenerating a seasoning liquid after pickling according to claim 1, which is operated while controlling the pH of the electrolyte solution in the concentrating chamber within the range of 4 to 10.