JP2001293380A - Method for preparing ion-exchange resin and regeneration method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare an ion-exchange resin, which absorbs and removes a group of a specific substance A, and avoids the adsorption-removal of specific two kinds of substances B and C. SOLUTION: An ion-exchange resin capable of adsorbing a group of the substance A is brought into contact with a solution in which the substances B and C are dissolved, and the substances B and C are ion-bonded with each other in 'a simultaneous bonding process'. An ion-exchange resin capable of adsorbing the group of the substance A is brought into contact with a solution of the substance B to prepare an ion-exchange resin bonded with the substance B, on the other hand, an ion-exchange resin capable of adsorbing the group of the substance A is brought into contact with the solution of the substance C to prepare an ion-exchange resin bonded with the substance C, and they are mixed at an appropriate ratio in 'a mixing process'. An ion-exchange resin capable of adsorbing the group of the substance A is brought into contact with a solution of the substance B and then with a solution of the substance C, and a homogenization treatment is carried out in 'a sequential bonding process'.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing and regenerating an ion exchange resin used for treating vegetable juice and the like.

[0002]

2. Description of the Related Art It has been generally practiced to obtain juice from a plant rich in vitamins, minerals, dietary fiber and the like, and to process the juice into food and drink. It is. However, in recent years, depending on the type of plant, when ingested by humans, a large amount of nitrate ions involved in the production of nitrite and nitroso compounds, which are undesirable for health in the body, are accumulated in the tissues in large amounts, reducing nitrate from plant-derived foods. It was pointed out that it was necessary to
Various methods such as an ion exchange method, an electrodialysis method, and a reverse osmosis membrane filtration method have been proposed as production methods for this purpose. Among them, the ion exchange method has an advantage that the nitrate ion removal efficiency is high and the equipment cost is relatively low.

[0003] The present inventors have focused on a method of reducing nitrate ions in plant juice by this ion exchange method, and have conducted an ion exchange process on a plant juice using a commercially available ion exchange resin. When treated, nitrate ions can be reduced, but at the same time, inorganic anions and organic acids are also adsorbed and removed, which has led to a significant decrease in palatability of plant juice. Currently unpublished). Therefore, the present inventors have developed a method for producing a vegetable juice that can efficiently reduce nitrate ions based on such knowledge and can maintain two types of component concentrations of an inorganic anion and an organic acid. The research has been advanced.

By the way, when the ion exchange treatment method disclosed in the prior art is examined, when a specific substance A group is to be adsorbed and removed from the target liquid, another specific substance B is adsorbed and removed. For example, JP-A-58-56663 discloses a method of performing a pretreatment for binding substance B to an ion-exchange resin, but a method of avoiding adsorption and removal of two specific types of substances. Has not yet been disclosed. Also, referring to other conventional techniques, for example, the invention described in JP-A-4-341153, a method of adding a shortage of the substance C to be adsorbed and removed together with the substance A group after the ion exchange treatment can be considered. This method is also used for the substance C that has been adsorbed and removed.
However, in view of the fact that the addition of the substance C itself and the recent consumer trends that prefer the natural form of natural products, the method of maintaining the substance C that the plant originally has is more preferable in consideration of the recent consumer trends and the like. Needless to say.

On the other hand, in consideration of productivity, it is necessary to sufficiently consider regeneration of an anion exchange resin after denitrification. Regarding the regeneration of the anion exchange resin, various anions including nitrate ions are adsorbed to the ion exchange groups of the anion exchange resin used for the contact treatment with vegetable juice. Of course, it is necessary to return to the substitution composition, but it is also particularly important to sufficiently wash and remove organic substances and suspensions derived from vegetable juice adhering to the base of the anion exchange resin. .

In view of the conventional method of regenerating an ion-exchange resin, particularly the method of regenerating an anion-exchange resin after treatment with a vegetable juice, an alkaline washing, In other words, it is considered good to pass aqueous sodium hydroxide solution, and acid cleaning is also effective. Therefore, generally, hydrochloric acid adjusted to a predetermined concentration is passed, or alkali cleaning and acid cleaning are performed. Washing such as passing a liquid in combination with washing has been performed.
Further, as the invention, for example, JP-A-8-242826 and JP-A-9-225 disclose a method of treating an anion exchange resin after vegetable juice treatment in the order of alkali washing, acid washing, and alkali washing, JP-A-11-29004
No. 1 discloses a method in which an anion exchange resin after vegetable juice treatment is treated with an aqueous solution of sodium hydroxide and then with an aqueous solution of sodium chloride. However, none of the conventionally proposed regeneration methods can provide a sufficient washing effect depending on the type of vegetables, and a proposal for a more effective regeneration method has been awaited.

Accordingly, the present invention provides an ion exchange resin capable of adsorbing and removing a specific substance A group and avoiding adsorption and removal of two specific substances B and C. An object of the present invention is to provide a method for producing an ion exchange resin and a method for regenerating such an ion exchange resin.

[0008]

According to the present invention, there is provided a method for treating a first ion-exchange resin, the method comprising:
A production method in which a substance B and a substance C are ion-bonded to the ion exchange resin by bringing an ion exchange resin capable of adsorbing the substance A group into contact with a solution in which the substance B and the substance C are both dissolved (hereinafter, this treatment The method is called "simultaneous binding method.")
Suggest. It should be noted that all of the substances A, B, and C in this specification indicate a specific substance, and the substance is meant to include an organic substance, an inorganic substance, an ion, and the like.

The simultaneous bonding method is particularly excellent in terms of efficiency because the substance B and the substance C can be treated at one time and the surplus substances B and C can be removed at one time.

The present invention also provides a method for treating a second ion-exchange resin as a solution in which substance B is dissolved (hereinafter referred to as “substance B”).
A solution. ) Is brought into contact with an ion-exchange resin capable of adsorbing the substance A group to form an ion-exchange resin to which the substance B is bonded, while a substance A is dissolved in a solution in which the substance C is dissolved (hereinafter referred to as a “substance C solution”). A method in which an ion-exchange resin capable of adsorbing a group is brought into contact to prepare an ion-exchange resin to which substance C is bound, and the ion-exchange resin to which substance B is bound and the ion-exchange resin to which substance C is bound are mixed at an appropriate ratio. A method (hereinafter, this processing method is referred to as “mixing method”) is proposed.

In this mixing method, the properties of the product obtained by the treatment can be adjusted by adjusting the mixing ratio of the ion exchange resin to which the substance B is bonded and the ion exchange resin to which the substance C is bonded. For example, when applied to the treatment of plant juice, it is particularly excellent in that the taste can be arbitrarily adjusted by adjusting the mixing ratio.

According to the present invention, as a third method for treating an ion exchange resin, an ion exchange resin capable of adsorbing a substance group A is brought into contact with a substance B solution, and then the ion exchange resin is treated with a substance C.
A production method in which the solution is brought into contact with a solution and then subjected to a homogenization treatment of the ion exchange resin (hereinafter, this treatment method is referred to as “sequential bonding method”) is proposed.

In this sequential bonding method, specifically, an ion-exchange resin is filled in a resin tower (the term "resin tower" in the present specification means a contact treatment device and includes a column or the like).
It can be carried out by allowing the solution of the substance B to flow down into the resin tower, then allowing the solution of the substance C to flow down to the resin tower, and then performing a homogenization treatment in the resin tower. Thus, the sequential bonding method is excellent in that all the processes can be performed in the same resin tower.

However, when the treatment is carried out in the same resin tower as described above, a bias may occur in the coupling ratio of the substances B and C between the upper layer and the lower layer of the resin tower, resulting in a stratified distribution. is assumed. For example, it is assumed that only the substance C is bonded to the ion exchange resin in the upper layer, and conversely, only the substance B is bonded to the ion exchange resin in the lower layer. Therefore, in the present treatment method, the ion exchange resin is subjected to a homogenization treatment after the contact step.

In the homogenization treatment, an appropriate means capable of stirring and homogenizing the ion-exchange resin in which the laminar distribution is generated can be adopted. For example, by sending a water stream, an air stream, or a water stream and an air stream to the ion exchange resin in a direction opposite to a contact direction of the solution in which the substance B is dissolved and the solution in which the substance C is dissolved. Can be.

After the solution in which the substance C is dissolved flows down into the resin tower as described above, the ion exchange resin may be transferred to another processing apparatus such as a resin tower or a tank by a water flow or the like. Good. At this time, since the ion exchange resin can be agitated by a water flow or the like, a homogenization treatment can be performed. If this alone is insufficient, homogenization of the resin is ensured by transferring the water stream, air stream, or water stream and air stream into another processing unit after transfer to another processing unit. It is preferred that

[0017] Further, in this sequential bonding method, the substance B
Another feature is that the substance B or the substance C can be replaced at a desired ratio with respect to the ion binding capacity of the ion exchange resin by adjusting the concentration of the solution in which the substance C is dissolved. . Specifically, a preferable binding ratio (substitution amount) of the substance B or the substance C to the ion exchange capacity of the ion exchange resin is determined, and the concentration of the substance B solution or the substance C solution is determined according to the preferable binding ratio (substitution amount). Can be adjusted. In this way, the amount of the substances B and C to be adsorbed and bonded to the ion exchange resin can be reduced to a necessary minimum. In this regard, in comparison with the simultaneous binding method, in the simultaneous binding method, a solution in which both the substance B and the substance C are dissolved is brought into contact with the ion exchange resin, and then a large amount of the substance B and the substance C are brought to a state of adsorption equilibrium. Since it is necessary to keep flowing, the sequential coupling method with concentration adjustment is particularly excellent in terms of running cost.

According to any of the above-mentioned methods for producing an ion exchange resin of the present invention, an ion exchange resin capable of adsorbing and removing the substance A group and avoiding the adsorption and removal of two kinds of substances B and C, That is, an ion exchange resin having a structure in which the substance B and the substance C are mixed and ion-bonded can be produced.

Next, in the present invention, as a method for regenerating an ion exchange resin, the used ion exchange resin is washed with an alkali salt solution (this is also referred to as "alkaline salt washing") and then any of the above. Processing, i.e., simultaneous binding, mixing,
A reproduction method characterized by performing any one of the sequential joining methods is proposed.

As a specific method of washing with an alkali salt, for example, a method of washing a used ion exchange resin with a mixed solution of an aqueous solution of sodium hydroxide and an aqueous solution of sodium chloride can be preferably exemplified. By performing the alkali salt washing in this manner, organic substances and impurities that could not be removed by the conventional alkali washing method can be effectively removed, and the adsorption capacity of the used ion exchange resin can be further recovered, A regeneration method suitable for continuous production and multi-lot production can be provided.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The method for treating and regenerating an ion-exchange resin of the present invention will be described below while removing nitrate ions (corresponding to the above-mentioned substance A) from a vegetable juice while adding an inorganic anion component to the above-mentioned substance B. Ion exchange resin used in a method for producing a vegetable juice in order to avoid the removal of organic acids (equivalent to the substance C) and to maintain the concentrations thereof, that is, at least one or more inorganic anions. A case where the present invention is applied to create and regenerate an anion exchange resin having a structure formed by ion-bonding a mixture of and an at least one organic acid is described.

Here, the plant of plant juice refers to a plant tissue or a plant body that has experienced eating, and the edible portion thereof is not particularly limited, and leaves, petiole, stem, root, flower, fruit (fruit and vegetable) ), Seeds, seeds, beans and the like.
Specifically, Apiaceae plants (parsley, celery, celery, honeybee, celeriac, carrot, kinsai, ashitaba, etc.), cruciferous plants (cabbage, radish, Chinese cabbage, broccoli, mustard, cauliflower, takanah,
Kyona, watercress, komatsuna, taisai, bok choy, turnip, wasabi, nabana, kale, etc., asteraceous plants (artichoke, shungiku, lettuce, butterbur, etc., sagebrush, mugwort, burdock etc.), lily plants (asparagus,
Leek, leek, leek, onion, garlic, lily, scallop, etc.), Ukogi (Udo, Tara tree, etc.), Lindenaceae (Moloheiya, etc.), Rutaceae (Sancho, citrus, etc.), Gramineae (barley) , Bamboo shoots, barley and the like), cruciferous plants (such as crucifers), Acatheaceae plants (such as spinach and beet), myrrhaceous plants (such as myrrhiza), lamiaceae plants (such as perilla), and solanaceous plants (such as eggplant, tomato, and pepper) , Peppers, paprika, etc.), mallow plants (okra, etc.), cucumber plants (cucumber, pumpkin, watermelon, melon, other cucurbits, etc.), pepper plants (pepper, etc.), camellia plants (cha), roseaceae Plants (strawberry, apple, etc.), legumes (soybean, kidney beans, peas, etc.), Rubiaceae plants (coffee, etc.), waterlily plants (lotus root, etc.), Youga Plants (ginger, etc.) and the like. Of these, Umbelliferae, Compositae family, is particularly effective for plant species nitrate content, such as Chenopodiaceae and cruciferous plants known for high.

The term "plant juice" includes juices, extracts, mixtures thereof, and concentrated or diluted solutions derived from at least one plant. I mean to. Combinations of plants having different degrees of drying, juice treatment and extraction treatment may be used in combination, or juice and extract may be mixed, or any combination thereof. For example, one of the above-mentioned combinations can be considered that, after extracting the undried plant tissue with water, the extracted residue is squeezed and the squeezed juice obtained is used as the plant juice.

The pH of the vegetable juice before contact with the anion exchange resin may be adjusted to a range in which the ion exchange reaction of the anion exchange resin can occur, and is neutral to acidic for suppressing deterioration of the juice properties. Is preferred. Further, it is preferable that the plant juice before contact with the anion exchange resin be inactivated or removed in advance for enzymes that destabilize its properties. If the treatment is performed in advance in this way, aggregation during the contact treatment with the anion exchange resin can be effectively prevented.

"Anion exchange resin" used in the production method
That is, the "anion exchange resin" constituting the basic skeleton of the anion exchange resin used in the contact treatment of the present invention is required to have an anion exchange ability and to be insoluble in plant juice. Yes, the form may be appropriately selected as appropriate for use, and may be, for example, a powdery form, a spherical form, a fibrous form, a film form, or another form. Either a strongly basic ion exchange resin or a weakly basic ion exchange resin can be used, and the shape of the resin matrix such as gel, porous, or high porous can be appropriately selected. In particular,
Diaion / SA series (SA10A, 11A, 12A, 20A
, 21A etc.), PA series (PA306,308,312,316,318,40
6,408,412,416,418 etc.), WA series (WA10,11,20,21,3
0 etc.), Amberlite / IRA series (IRA-400, 41
0, 900, 93ZU, etc.).

Next, examples of the "inorganic anion" to be bound to the anion exchange resin include chloride ion, sulfate ion, nitrate ion, nitrite ion, phosphate ion and the like. If considered, nitrate and nitrite should be excluded from the selection. Also,
Considering the effect on palatability and the content rate in plants,
It is preferable to contain at least one or more selected from chloride ions and sulfate ions. Further, considering the safety and solubility in use, it is preferable to use sodium salts, potassium salts, and the like of these ions. preferable.

"Organic acid" bound to an anion exchange resin
Examples thereof include citric acid, malic acid, tartaric acid, lactic acid, L-ascorbic acid, fumaric acid, gluconic acid, acetic acid, adipic acid, and the like, which are not particularly limited as long as they do not interfere with food addition. Absent. Oxalic acid, which is widely present in plants, is liable to form calcium and precipitates, and is a causative substance that lowers the stability of properties and palatability.

In order to prevent an extreme change in taste, it is preferable that the composition of the original plant juice is not extremely changed. Therefore, generally, inorganic anions contained in plants include: Excluding nitrate ion, it contains a lot of chloride ion and then sulfate ion, and organic acid contains a lot of malic acid or citric acid.
In consideration of these points, it is preferable to use a combination of an inorganic anion and an organic acid of the type described herein for those that are previously ion-bonded to the anion exchange resin.

(Simultaneous Bonding Method) In the simultaneous bonding method, first, an anion exchange resin is brought into contact with a solution in which both an inorganic anion and an organic acid are dissolved (this step is referred to as a "contact step"). In this contacting step, for example, after filling the anion exchange resin in the column, an aqueous solution in which both the inorganic anion and the organic acid are dissolved is injected from the column entrance,
The aqueous solution may be continuously passed through the column until the component composition of the effluent obtained from the column outlet is substantially the same as the aqueous solution before passing through the column.

Following the contacting step, it is preferable to wash and remove excess anions (this step is referred to as “excess acid removing step”). Around the anion exchange resin immediately after performing the contacting step, there are extra anions such as inorganic anions and organic acids that are not chemically bonded to the anion exchange resin. Since there is a possibility of affecting the palatability, pH, and the like, it is preferable to wash and remove it. That is, this excess acid removal step is a treatment step for preventing the presence of excess inorganic anions or organic acids that are expected to be present from being mixed into the vegetable juice and affecting its taste, pH, etc. Therefore, the higher the washing accuracy is, the more preferable it is, but it is only necessary to wash to the extent that the influence of mixing into the vegetable juice is hard to appear, specifically, until the acidity of the washing effluent falls below at least 0.05%. It is desirable to use deionized water.

Here, washing with water until the acidity is less than 0.05% requires a large amount of water and time, so there is a slight difficulty in efficiency. As a method of improving this, the following method can be mentioned from the relationship between the aqueous solution used in the acid contact step and the ion exchange capacity of the anion exchange resin. When using a weakly basic anion exchange resin as the anion exchange resin,
Due to the weak neutral salt resolution of weakly basic anion exchange resin,
It is conceivable to supply these as an acid (hydrochloric acid, citric acid aqueous solution, etc.) for ion-bonding the inorganic anion and the organic acid. However, it is extremely difficult to remove the anion in the subsequent excess acid removing step, and after all, Since a large amount of water is required, when using a weakly basic anion exchange resin, a small amount of an extremely dilute aqueous alkali solution is brought into contact with the resin before the excess acid removing step, and the pH of the solution around the ion exchange resin is adjusted to a medium level. It is preferable to reduce the amount of washing water used thereafter by summing. However, this method has a problem that the number of steps is increased. On the other hand, when a strongly basic ion exchange resin is used as the anion exchange resin, the ions to be bound are supplied as an acid, and the neutralization treatment is performed before the excess acid removal step as described above to reduce the amount of water used. It is preferable in doing. After all, the most preferable is to use a strongly basic ion exchange resin as the anion exchange resin, and to adjust the pH of the aqueous solution that is the source of the inorganic anions and organic acids to be ion-bonded.
Is adjusted to be neutral. If you do this,
It is not necessary to perform a neutralization treatment before the surplus acid removing step, and the washing can be performed by using a small amount of water. That is, this is a method in which an aqueous solution used in the acid contacting step is neutralized and ion exchange is carried out utilizing the neutral salt decomposability of a strongly basic anion exchange resin or the like. This preparation method includes the steps of preparing an aqueous solution of an inorganic salt represented by a sodium salt, a potassium salt, and an ammonium salt of various inorganic anions and an organic acid salt represented by a sodium salt, a potassium salt, and an ammonium salt of various organic acids. Or a method in which an alkali component such as sodium hydroxide or potassium hydroxide is added to an inorganic anion, and a solution in which an alkali component such as sodium hydroxide or potassium hydroxide is added to an organic acid aqueous solution A method of adjusting the pH to neutral with the above method or a method combining these methods can be preferably exemplified.

(Sequential bonding method) In the sequential bonding method, after filling an anion exchange resin in a resin tower, an inorganic anion replacement step is carried out.
It can be performed by sequentially performing the organic acid substitution step and the ion exchange resin homogenization step.

As the anion exchange resin to be filled in the resin tower in this bonding method, the above-mentioned anion exchange resin can be used, but the nitrate ion removal effect is further obtained.
It is more preferable that the resin tower be shaped so that it can be filled in the resin tower and a sufficient stirring effect can be obtained by upward flow or the like. However, it is preferable to select a strongly basic porous resin in consideration of more effective treatment, that is, the resolution of neutral salt, detergency and physical strength. As the anion exchange resin corresponding to this, Diaion PA series (I type: PA306,308,312,316,318)
And II type 406, 408, 412, 416, 418 etc.). Among them, the I type is preferable in consideration of heat resistance.

In the “inorganic anion replacement step”, for example, an aqueous solution in which at least one or more inorganic anions are dissolved is caused to flow down into the resin tower, and is brought into contact with the anion exchange resin in a downward flow. What should I do? At this time, the inorganic anion preferably contains at least one or more selected from chloride ions and sulfate ions in consideration of the content in plants and the like. When it is desired to replace a plurality of types of inorganic anions, a method of treating with a mixed aqueous solution containing all the ions to be replaced, or after performing one type of ion replacement, separately using another type of ion alone in a required amount Although the method of substitution etc. can be mentioned, the latter is preferable in that the substitution amount can be easily controlled.

In the next “organic acid substitution step”, an aqueous solution in which at least one or more organic acids are dissolved is allowed to flow down into the resin tower, and is brought into contact with the anion exchange resin in a downward flow. Is preferred. At this time, the concentration of the solution in which the organic acid is dissolved is replaced by 5 to 95% of the ion binding capacity of the anion exchange resin, assuming that the entire amount of the organic acid aqueous solution flows through the anion exchange resin. It is preferable to adjust so that By adjusting the concentration in this manner, an organic acid can be ionically bonded to 5 to 95% of all ion exchange groups of the anion exchange resin. Also, the pH of the organic acid aqueous solution
Is preferably adjusted in the range of 3.7 to 5.3, particularly in the range of 4.4 to 5.0. When the pH is higher than 5.3, a phenomenon in which the pH of the plant juice is significantly increased when the plant juice is subjected to the denitrification treatment is observed, and it may be necessary to readjust the pH of the plant juice after the treatment. On the other hand, when the pH is lower than 3.7, the organic acid is not sufficiently adsorbed on the resin during the organic acid substitution step, and the organic acid is discharged outside the resin tower and a predetermined substitution amount cannot be obtained. It can be wasted. When it is desired to substitute plural kinds of organic acids, two methods can be proposed as in the case of the plural kinds of treatment in the inorganic anion substitution step.
It is better to select a method of replacing species by species.

Here, when the inorganic anion substitution step and the organic acid substitution step are performed in a resin tower, various solutions remain in the resin layer. Preferably, the remaining solution is washed.

Then, in the next “ion exchange resin homogenization step”, the anion exchange resin in the resin tower can exhibit a somewhat uniform ion exchange treatment effect.
The anion exchange resin in which the stratified distribution occurs in the resin tower is stirred and homogenized. This is presumed that a layered distribution occurs due to the type of anions substituted in the resin layer by the inorganic anion substitution step and the organic acid substitution step. In other words, in simple terms, the anion exchange resin in the lower layer is mainly replaced with an inorganic anion, the resin in the upper layer is mainly replaced with an organic acid, and the resin in the intermediate layer is an inorganic anion and an organic acid. It is supposed that the plant juice is denitrified in such a state because it is supposed to be mixed and replaced, so it seems to secure the concentration of the target inorganic anion and organic acid in this state This is because the pre-processing may not be meaningful.

The homogenization of the anion exchange resin is carried out by, for example, flowing upward from the lower end of the resin tower in a direction opposite to the contact direction of the inorganic anion and the organic acid with the anion exchange resin. Or by sending a stream of air.
Although it is possible to stir mechanically, this method is superior in that it does not damage the anion exchange resin and can be carried out efficiently at low cost. Above all, the air flow is relatively easy and sufficient to stir the resin layer by applying a large air pressure, and therefore is excellent in terms of the stirring effect, cost and simplicity. In fact, when an air flow and a water flow were sent upward in a resin tower having a height of about 140 cm and compared, a result was obtained that the air flow could more easily obtain the stirring effect. It is also possible to use both a water stream and an air stream.

After the organic acid substitution step, the ion exchange resin may be transferred to another processing apparatus such as a resin tower or a tank. At this time, if the ion exchange resin is transferred by a water flow or the like, the ion exchange resin can be simultaneously homogenized. However, if this alone is not enough for homogenization,
What is necessary is just to perform the same homogenization processing again in the said another processing apparatus.

After the resin homogenization treatment, the bubbles remaining in the resin layer are discharged only by the upward water flow before contact with the vegetable juice, and the entire resin layer is allowed to settle so that the vegetable juice flows uniformly. desirable.

If the plant juice is denitrified using the anion exchange resin treated by such a sequential binding method, not only can nitrate be removed sufficiently, but also the palatability is excellent, and It is possible to obtain a plant juice product in which fluctuations in color tone and the like in multi-lot production are minimized.

(Method of Regenerating Spent Ion Exchange Resin) The method of regenerating a used ion exchange resin proposed by the present invention is to wash the used ion exchange resin with an alkali salt, and then perform the above simultaneous bonding method, mixing method, and the like in order. This is a method of performing any one of the processes of the joining method.

As a specific method of washing with an alkali salt, it is preferable to wash the used ion-exchange resin with a mixed solution of an aqueous solution of sodium hydroxide and an aqueous solution of sodium chloride. 2-8%
Preferably, a solution adjusted to about 4% is used. As the aqueous sodium chloride solution, one adjusted to 8 to 12%, preferably to about 10% is used, and these are adjusted to 0.5: 2 to 3: 2,
Preferably, washing is performed with a mixed aqueous solution mixed at about 1: 2. At this time, it is preferable to wash with a mixed aqueous solution of about 1 to 6 times, preferably about 4 times the amount of the resin.

The alkali component adhering to the resin by washing with an alkali salt is thoroughly washed with water or neutralized with hydrochloric acid or the like and washed, and then the method for producing the ion exchange resin of the present invention is carried out. May be carried out to produce an anion exchange resin used in a method for producing vegetable juice. Further, it is preferable that the mixed aqueous solution of sodium hydroxide and sodium chloride is controlled at about 40 ° C. to about 60 ° C., and the mixed aqueous solution is controlled at this temperature for washing. Actually, as compared with the case without heating, it was confirmed that the degree of resin coloring was obviously reduced. More specifically, it is preferable to pass a mixed aqueous solution of sodium hydroxide and sodium chloride controlled at about 40 ° C. to about 60 ° C. through the resin layer, and pass the solution until the outlet liquid temperature becomes about 40 ° C. . It is more effective if the processing is performed so that a processing time of one hour or more is required.

When washing with an alkali salt,
It is preferable not to carry out the backwashing after the denitrification treatment, or to carry out the backwashing to such an extent that the resin layer is not largely disturbed even if the backwashing is carried out, and thereafter carry out the alkali salt washing in an upward flow.
With this configuration, the resin layer slightly flows, the contact between the chemical solution and the resin can be performed efficiently, and the resin upper layer having a high degree of coloring can be positioned downstream during the alkali salt washing. Can perform more effective cleaning,
It is possible to further reduce the coloring of the resin, that is, the degree of adhesion of organic substances and impurities. The backwashing for the purpose of removing the suspended matter may be carried out after that, and more preferably, hot water of about 40 ° C. to about 60 ° C. is also flowed during the backwashing. On the other hand, when the alkali salt washing is performed in the downward flow, it is preferable to carry out backwashing at a sufficient flow rate in advance to achieve the removal of the suspended matter and the stirring of the resin, and the completion of the alkali salt washing. It is more preferable to perform hot water washing later.

Here, the results of actual comparison between the conventional alkali cleaning and the alkali salt cleaning of the present invention will be described. When the clear celery concentrated juice was denitrified with a porous anion exchange resin (PA316 (white)) in which chloride ions and malic acid were ionically bonded, dye adsorption from celery was observed on the anion exchange resin. The uppermost layer of the resin layer turned from black-brown to brown, and deep yellow adsorption was observed downward. Therefore, in order to regenerate the used anion exchange resin, alkali washing (4% aqueous sodium hydroxide solution, 4 times the amount of the resin passed) is performed, and then sufficient water washing is performed. Tried to perform chlorine substitution. Then, the adsorbed nitrate ions could be sufficiently removed, and the coloration state of the resin due to the attachment of impurities could be greatly improved, but the pale brown coloration was maintained at the upper layer of the resin, and became thinner toward the lower layer. It became a light yellow colored state. This coloration state is expected to affect the ability of the resin matrix to adsorb organic substances typified by the pigment component, and in consideration of the color tone management in the continuous production of vegetable juice products and the production of multiple lots, the washing effect is further improved. A high regeneration method was desired. On the other hand, the same used anion exchange resin was washed with a mixed aqueous solution (4 times the amount of the resin) obtained by mixing a 4% aqueous sodium hydroxide solution and a 10% aqueous sodium chloride solution at a ratio of 1: 2. Then, after sufficient water washing, chlorine replacement with an aqueous solution of sodium chloride was carried out.
Despite being reduced to / 3, a higher organic substance removing effect was observed, and the coloration state due to resin adsorption of the dye component was significantly reduced as compared with the case of alkali washing. Specifically, the resin layer can be washed to a very light yellowish white color as a whole, and although a slightly brown color remains in the upper layer portion, it is clearly lighter compared to the degree of coloring remaining in the resin upper layer portion during alkali cleaning. there were.

As a substitute for sodium hydroxide and sodium chloride used for washing with an alkali salt, potassium hydroxide, potassium chloride and the like can be used. In order to obtain a further cleaning effect, it is effective to carry out acid cleaning with hydrochloric acid or the like. This acid washing is preferably carried out between the denitrification step and the alkali salt washing step, or between the alkali salt washing step and the inorganic anion replacement step.

As a place where the step of regenerating the anion exchange resin is performed, an ordinary resin tower is suitable, and it is more preferable that the resin tower is equipped with a facility capable of backwashing. Among the ion exchange resins of the present invention, the sequential bonding method can carry out the various steps in the same resin tower. Therefore, following the sequential bonding method, the regeneration method of the present invention is also performed in the same resin tower as it is. It can also be implemented. In addition, we install reproduction-only tower,
It is also possible to transfer the used resin and carry out the process in a regeneration tower. Furthermore, the steps of the binding method and the regeneration method can be carried out by appropriately sharing the steps of the plant juice denitrification treatment tower and the regeneration-only tower.

Hereinafter, the present invention will be described in comparison with Examples and Comparative Examples.

-Examples and Comparative Examples in the Simultaneous Binding Method- (Comparative Example 1)
After slicing in a width of 90 m and boiled in ion-exchanged water at 90 ° C. for 15 minutes, the mixture was crushed and squeezed with a juicer mixer, pulp was removed by centrifugation, and then Br was evaporated with an evaporator.
ix36 (about 6-fold concentration), and the obtained concentrated liquid was filtered with absorbent cotton to obtain an orange concentrated juice.

(Comparative Example 2) The concentrated juice obtained in Comparative Example 1 was used, and 100 ml of this juice was used as an anion exchanger (strongly basic anion exchange resin, IRA400.
(40 ml) in a column manner to obtain an ion-exchanged juice. In preparing an anion exchanger to which chloride ions were bound, a 10% aqueous NaCl solution was passed through the anion exchanger packed in the column in an amount equivalent to 5 times the volume of the ion exchanger. This was washed with ion-exchanged water, and this was carried out until the acidity of the washing wastewater became less than 0.05%, to obtain the above-mentioned anion exchanger.

Comparative Example 3 The concentrated juice obtained in Comparative Example 1 was used, and 100 ml of this juice was used as an anion exchanger bound with malic acid (strongly basic anion exchange resin, IRA400.4).
0 ml) in a column manner to obtain an ion-exchanged juice. In preparing the anion exchanger to which malic acid was bound, a 15% aqueous solution of sodium malate was passed through the anion exchanger packed in the column in an amount equivalent to 5 times the volume of the ion exchanger. Thereafter, washing with ion-exchanged water was carried out until the acidity of the washing wastewater was less than 0.05%, to obtain the above-mentioned anion exchanger.

Example 1 Using the concentrated juice obtained in Comparative Example 1, 100 ml of this juice was mixed with chloride ion, sulfate ion, malic acid and acetic acid in a ratio of 5: 2: 12: 3 (molar). The mixture was subjected to continuous contact treatment by a column method using an anion exchanger (strongly converted anion exchange resin, IRA400, 40 ml) ion-bonded in terms of (in terms of conversion) to obtain an ion-exchanged juice. In preparing an anion exchanger in which an inorganic anion and an organic acid are bonded, an aqueous solution in which the inorganic anion and the organic acid are dissolved in the above molar ratio with respect to the anion exchanger packed in a column ( 15% W / V) was passed through, equivalent to 5 times the volume of the ion exchanger, and then washed with ion-exchanged water until the acidity of the washing wastewater was less than 0.05%. An ion exchanger was obtained.

(Evaluation 1) The ion-exchanged juices prepared in Comparative Examples 1, 2, and 3 and Example 1
The rix value was adjusted to 6.0, and the nitrate value and taste were evaluated. The results are shown in Table 1 below. In all the samples subjected to the ion exchange, a remarkable nitrate ion removing effect was exhibited, but in Comparative Examples 2 and 3, the change in taste was large and the original taste of carrot was not retained. In particular, Comparative Example 2
In Comparative Example 3, the saltiness and saltiness became strong, and in Comparative Example 3, there was no richness, and the taste became thin as diluted with water. On the other hand, in Example 1, the tendency of the body to weaken slightly was observed,
Considering that the original taste found in Comparative Example 1 is sufficiently provided, the quality is good enough to be used as a straight juice, and the nitric acid value can be reduced, it is more comprehensive than Comparative Example 1. The quality can be judged to be excellent.

[0055]

[Table 1]

(Evaluation 2) Next, the juices in Comparative Example 1 and Example 1 were diluted to Brix 6.0, and the amount of change in each component was examined. The results are shown in Table 2. In the sample of Example 1, although the nitrate ion content was remarkably reduced, chlorine, sulfuric acid, potassium ion, and the highest concentration organic acid (malic acid) did not fluctuate greatly, and the nitrate ion was selectively removed. Removal had been done. In addition, due to the mixed ion exchange between the inorganic anion and the organic acid, the nitrate ion value is lower than the sum of the chloride ion and the sulfate ion and the value of the organic acid showing the highest concentration. At the same time, the nitrate ion / potassium ion ratio showed an extremely low value of 0.002.

[0057]

[Table 2]

(Comparative Example 4) Boiled celery leaves and petiole with ion-exchanged water at 90 ° C for 2 minutes, crushed and squeezed with a juicer mixer, and removed pulp by centrifugation.
The mixture was concentrated to Brix 20 using an evaporator, and the obtained concentrate was filtered with absorbent cotton to obtain a concentrated juice.

(Example 2) The concentrated juice obtained in Comparative Example 4 was used, and 100 ml of this juice was mixed with an anion exchanger (maleic acid) in which malic acid and chloride ion were bonded at a molar ratio of 4: 1. An ion exchange treatment was performed on a column packed with an ion exchange resin (PA316, 40 ml) to obtain an ion-exchanged juice. The anion exchanger used was a 15% (W / V) aqueous solution adjusted to malic acid: chlorine = 4: 1 (in terms of molar concentration). , And then washed with ion-exchanged water until the acidity of the washing wastewater was less than 0.05% to obtain the anion exchanger.

(Evaluation 3) The celery juice in Comparative Example 4 and Example 2 was diluted to Brix 2.0, and the amount of change in each component was examined. The results are shown in Table 3. In the sample of Example 2, a high concentration of nitrate ion was efficiently converted into chloride ion and malic acid, and therefore, an increase in the concentration of chloride ion and malic acid (the highest concentration organic acid) was confirmed. However, this increase in concentration did not significantly change the original composition balance. In addition, the nitrate ion value is lower than the sum of the chloride ion and the sulfate ion and the chemical equivalent concentration of the organic acid showing the highest concentration,
The ratio of nitrate ion / potassium ion was extremely low at less than 0.00037.

[0061]

[Table 3]

(Comparative Example 5) The celery juice prepared in Comparative Example 4 adjusted to Brix 2.0, the carrot juice prepared in Example 1 adjusted to Brix 18.0, and ion-exchanged water were each stored in a volume. The mixture was mixed at a ratio of 1: 2: 3 to prepare a mixed juice.

(Example 3) The celery juice prepared in Example 2 was adjusted to Brix 2.0, the carrot juice prepared in Example 1 was adjusted to Brix 18.0, and ion-exchanged water was replaced by a volume. The mixture was mixed at a ratio of 1: 2: 3 to prepare a mixed juice.

(Evaluation 4) The nitrate ion value and taste of the mixed juices prepared in Comparative Example 5 and Example 3 were evaluated. The results are shown in Table 4.

[0065]

[Table 4]

Example and Comparative Example in Sequential Coupling Method Example 4 Porous anion exchange resin (PA316 (white)) in which chloride ion and malic acid are mixed and ion-bonded
, A transparent celery concentrated juice of Brix20 (1 time the amount of the resin) was passed downflow at a flow rate of SV = 5 / h in a column packed with to carry out denitrification treatment.

The "anion exchange resin formed by mixing and ionizing chloride ions and malic acid" used at this time was first replaced with chlorine by exchanging all the exchange groups by passing an aqueous solution of sodium chloride. Malic acid having a chemical equivalent equivalent to 75% of the capacity (1.3 meq / ml-R, from the product standard value) is dissolved in 5 times the amount of water of the resin amount, adjusted to pH 4.8, and then adjusted to the flow rate SV. = 5 / h to complete the substitution of the organic acid, then wash the resin layer with water, perform the substitution composition homogenization step with upwardly flowing water, settle, and then denitrate. It was used for.

After the denitrification treatment, the ion-exchange resin
Aqueous solution (17 ° C.) obtained by mixing 1: 2 aqueous sodium hydroxide solution and 10% aqueous sodium chloride solution at a flow rate of 4 times the amount of the resin in a downward flow, SV = 4 / h, and then sufficiently washing with water Was carried out, and chlorine substitution was carried out with a 10% aqueous sodium chloride solution.

(Example 5) An anion exchange resin after denitrification was obtained in the same manner as in Example 4, and this was mixed with a 4% aqueous sodium hydroxide solution and a 10% aqueous sodium chloride solution in a constant temperature room controlled at 40 ° C. Aqueous solution (60
° C) was passed upward in a flow rate of 4 times that of the resin and SV = 4 / h, and then sufficiently washed with water at room temperature, followed by purging with 10% aqueous sodium chloride.

(Comparative Example 6) An anion exchange resin after denitrification was obtained in the same manner as in Example 4, and this was subjected to a 4% aqueous solution of sodium hydroxide (20 ° C.) in a downward flow in an amount 4 times the amount of the resin. SV =
After passing 4 / h of the liquid, and after sufficient water washing, 10
% Sodium chloride aqueous solution was used for chlorine substitution.

(Evaluation 5) The degree of coloring of the resin layers obtained in Example 4 and Example 5 and the resin layer obtained in Comparative Example 6 was compared and evaluated.
The cleaning effect was evaluated. In the resin after washing obtained in Comparative Example 6, the light brown colored state was maintained in the upper layer portion of the resin, and the resin became a light bright yellow color as it became lower. In the resin obtained in Example 4, the resin layer exhibited a pale yellowish-white color, and the upper layer portion tended to be slightly brownish. In the resin obtained in Example 5, the entire resin layer had a pale yellowish-white color, and almost no brown coloration was observed in the resin upper layer. The relationship of Comparative Example 6> Example 4> Example 5 was established as the coloring strength relationship of these resins.

(Example 6) In a column filled with an anion exchange resin (PA316) in which chloride ions and malic acid were mixed and ion-bonded, a clear spinach concentrate (Br) was added.
(× 20, pH 4.95) in a downward flow at a flow rate SV = 5 / h, 4 times the amount of the resin, and a denitrification treatment was carried out.

Here, the “anion exchange resin in which chloride ions and malic acid are mixed and ion-bonded” is obtained by first exchanging all the exchange groups with chlorine by passing an aqueous solution of sodium chloride and then exchanging the exchange capacity of the resin. Malic acid having a chemical equivalent of 75% (1.3 meq / ml-R, from product standard value) is dissolved in 5 times the amount of resin in water, and after adjusting to various pH values, The solution was passed at SV = 5 / h to complete the organic acid substitution. Thereafter, a substitution composition homogenization step was performed by flowing water upward, and the mixture was settled, and then used for denitrification treatment.

Effluent from organic acid flow-through treatment (organic acid waste liquid)
Was collected and the amount of malic acid released was measured, and the denitrification treatment was carried out in the treated section where the amount of discharged malic acid was small. Then, when the concentration of the spinach concentrated juice discharged from the column exceeds Brix5, the recovery is started, and every two times the resin amount (樹脂 2 bed vo
l., ４4 bed vol.) and the pH of this concentrated solution was measured. Table 5 shows the results.

[0075]

[Table 5]

From the results shown in Table 5, the pH of the organic acid aqueous solution in the organic acid substitution step was adjusted to 3.7 or more.
Although the amount of organic acid discharged into the effluent can be reduced to less than 10% of the treatment amount, considering the increase in pH of the treated sample,
It turned out that it is preferable to adjust the organic acid aqueous solution to 5.3 or less.

Claims (12)

[Claims] 1. A method for producing an ion exchange resin for preparing an ion exchange resin capable of adsorbing and removing the substance A group and avoiding adsorption and removal of two kinds of substances B and C. And contacting an ion exchange resin capable of adsorbing the substance A group with a solution in which the substance B and the substance C are both dissolved, and ion-bonding the substance B and the substance C to the ion exchange resin. A method for producing an ion exchange resin. 2. A method for producing an ion exchange resin for preparing an ion exchange resin capable of adsorbing and removing the substance A group and avoiding the adsorption and removal of two kinds of substances B and C. An ion exchange resin capable of adsorbing the substance A group is brought into contact with a solution in which the substance B is dissolved to form an ion exchange resin in which the substance B is bonded, while a substance C is dissolved in the solution in which the substance C is dissolved. A
An ion exchange resin capable of adsorbing the group is brought into contact to prepare an ion exchange resin to which the substance C is bound, and the ion exchange resin to which the substance B is bound and the ion exchange resin to which the substance C is bound are mixed at an appropriate ratio. A method for producing an ion exchange resin, comprising: 3. A method for producing an ion exchange resin for preparing an ion exchange resin capable of adsorbing and removing the substance A group and avoiding adsorption and removal of two kinds of substances B and C. Contacting an ion exchange resin capable of adsorbing substance A with a solution in which substance B is dissolved, and then contacting the ion exchange resin with a solution in which substance C is dissolved; A method for producing an ion-exchange resin, comprising performing homogenization treatment of the resin. 4. The method according to claim 1, wherein the substance B or the substance C is replaced at a desired ratio with respect to the ion binding capacity of the ion exchange resin.
The method for producing an ion exchange resin according to claim 3, wherein the concentration of the solution in which the substance B or the substance C is dissolved is adjusted. 5. After filling a resin tower with an ion-exchange resin capable of adsorbing substance A, a solution in which substance B is dissolved is allowed to flow down into the resin tower, and then substance C is introduced into the resin tower. The method for producing an ion-exchange resin according to claim 3 or 4, wherein the dissolved solution is allowed to flow down, and thereafter, the homogenization treatment is performed in the resin tower. 6. The homogenization treatment according to claim 1, wherein the ion exchange resin has a water flow, an air flow, or a water flow in a direction opposite to a contact direction of the solution in which the substance B is dissolved and the solution in which the substance C is dissolved. The method for producing an ion exchange resin according to any one of claims 3 to 5, wherein the method is performed by sending an air flow. 7. A resin tower is filled with an ion-exchange resin capable of adsorbing substance A, and then a solution in which substance B is dissolved flows down into the resin tower, and then substance C is introduced into the resin tower. The method for producing an ion-exchange resin according to claim 3 or 4, wherein the dissolved solution is caused to flow down, and thereafter, the ion-exchange resin is transferred to another processing apparatus such as a resin tower or a tank by a water stream. 8. After the ion exchange resin is transferred to another processing apparatus, the resin is homogenized by sending a water stream, an air stream, or a water stream and an air stream in the another processing apparatus. A method for producing the ion exchange resin according to claim 7. 9. An ion exchange resin capable of adsorbing and removing nitrate ions and avoiding adsorption and removal of at least one or more inorganic anions and at least one or more organic acids. A method for producing an ion-exchange resin for contacting a solution in which an inorganic anion is dissolved with an anion-exchange resin, and then contacting the anion-exchange resin with a solution in which an organic acid is dissolved, Next, a homogenization treatment of the anion exchange resin is carried out. 10. The concentration of a solution in which an organic acid is dissolved,
The method for producing an ion exchange resin according to claim 9, wherein adjustment is performed so that the ion exchange capacity is replaced by 5 to 95% of the ion binding capacity of the anion exchange resin. 11. The method according to claim 9, wherein the pH of the solution in which the organic acid is dissolved is adjusted to a range of about 3.7 to 5.3. 12. A method for regenerating an ion-exchange resin, comprising washing the used ion-exchange resin with an alkali salt solution, and then performing the treatment in the method according to any one of claims 1 to 11. .