JPH0687984B2 - Rotary column ion exchanger with built-in ion exchange resin and ion exchange treatment method using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention aims at desalting cheese whey, skim milk, etc. using a rotary column ion exchanger containing an ion exchange resin. The present invention relates to a method for performing an ion exchange treatment of liquid or the like. The present technology is particularly suitable for continuous ion exchange treatment.

[Prior art and problems]

Ion exchange treatment technology for exchanging or eliminating ions in a liquid using an ion exchange resin is generally well known,
In fact, it is widely used in processes such as neutralization of reaction systems, desalting of liquids, and purification by removing ionic impurities. Ion exchange treatment with such an ion exchange resin is usually performed using a packed bed type reactor, which is generally considered to have good reaction efficiency. In this case, a cation exchange resin and an anion exchange resin are combined into one resin. There are a method of putting them in a tower and a mixed bed, and a method of putting them in different resin towers and making a mixed bed. However, in either of the packed bed reactors, there is a problem that the resin in the packed bed is densified and a channeling flow is apt to occur, which causes a decrease in ion exchange efficiency due to a decrease in contact efficiency. Further, when the ion exchange resin is regenerated, it is necessary to loosen and disperse the solidified packed layer in order to effectively regenerate the ion exchange resin, and in many cases, there is a problem that manual stirring is required.

That is, in the conventional ion exchange treatment by the packed bed reactor, there are problems such as a decrease in ion exchange efficiency due to channeling or the like that occurs during the ion exchange treatment, and the complexity of the regeneration treatment after the ion exchange treatment, This has become a serious issue in achieving efficiency, simplification, and continuity of processing.

On the other hand, the applicant of the present application has already proposed a reactor including a rotary column containing an immobilized enzyme as an active reactor capable of realizing the efficiency of a reaction system using the immobilized enzyme (JP 55-37130 gazette).

The present invention has been made in view of the above-mentioned problems of the prior art, and provides an ion exchanger and a method thereof that enable efficient ion exchange treatment by applying the basic principle of the above rotary column. Is.

[Means for Solving the Problems]

The present invention, firstly, an ion exchange resin is housed in an ion exchange treatment chamber sandwiched between an outer peripheral porous member and an inner peripheral porous member, and the peripheral diameter of the ion exchange treatment chamber is longer than the length in the rotation axis direction. A rotary column having a shape and a hollow shaft having a liquid supply / discharge orifice in a portion of the rotary shaft, and a rotary column internally rotatably adjustable and provided with a liquid supply / discharge pipe A rotary column ion exchanger with a built-in ion exchange resin, which comprises at least a column container comprising the following: Second, including the following steps performed using the rotary column ion exchanger with a built-in ion exchange resin Is an ion exchange treatment method.

Step: While rotating the rotary column, the ion exchange resin deposition layer forming liquid is supplied from the outer peripheral porous member side through the liquid supply / discharge pipe, and the inner peripheral porous member side is supplied through the hollow shaft. By discharging the liquid, an ion exchange resin deposition layer is formed on the inner peripheral porous member.

Step: The ion exchange treatment is carried out by continuing the rotation of the rotary column, supplying the liquid to be treated from the liquid supplying / discharging pipe, passing through the deposit layer, and discharging it from the hollow shaft.

Step: recovering the treatment liquid, then supplying the liquid for ion exchange regeneration into the rotary column through the hollow shaft, and at the same time, rotating the rotary column at a higher speed to destroy the deposited layer, Disperse.

Thirdly, another ion exchange treatment method is carried out by using the rotary column ion exchanger with a built-in ion exchange resin, which is characterized by including the following steps.

Process: While rotating the rotary column, the ion exchange resin deposition layer forming liquid is supplied from the inner peripheral porous member side via the hollow shaft, and the outer peripheral porous member side via the liquid supply / discharge pipes as necessary. Then, the liquid is discharged to form an ion exchange resin deposition layer on the outer peripheral porous member.

Step: The ion exchange treatment is performed by continuing the rotation of the rotary column, supplying the liquid to be treated from the hollow shaft, passing it through the deposition layer, and discharging it from the liquid supply / discharge pipe.

Step: recovering the treatment liquid, and then supplying a liquid for ion exchange regeneration into the rotary column through a liquid supply / discharge pipe, and at the same time rotating the rotary column at a slower speed Destroy and disperse the deposited layer.

According to the method of the present invention, while maintaining the effect of suppressing or preventing the occurrence of channeling, which is a characteristic of the rotary column, it is possible to form a deposition layer in the rotary column and realize an efficient ion exchange treatment, Further, it becomes possible to remarkably improve the efficiency of the regeneration treatment of the ion exchange resin, which has been a particularly problematic issue in the past.

There are roughly two methods for performing the ion exchange treatment using the ion exchanger of the present invention, and the liquid flow in the column is the outer circumference → center and the center → outer circumference, respectively.

First, a rotary column ion exchanger of the present invention will be described with reference to the drawings.

FIG. 1 is a schematic perspective view showing an embodiment of a rotary column ion exchanger before incorporating an ion exchange resin according to the present invention. Here, the ion exchange resin before being incorporated is shown, but it is because it may hinder understanding of the configuration if the ion exchange resin is drawn in a state before operation. A space sandwiched between the outer peripheral porous member 2 and the inner peripheral porous member 1 is an ion exchange processing chamber 6 in which an ion exchange resin is stored. Further, in this figure, although not an essential element, four porous partition plates 9 are provided to prevent uneven distribution of the ion exchange resin, and the ion exchange treatment chamber is divided into four chambers. The liquid flow passes through a hollow shaft 3 having a liquid supply / discharge orifice and a liquid supply / discharge pipe 4. The outer peripheral porous member 2 and the inner peripheral porous member 1 are integrated, and the hollow shaft 3 and the porous member are called a rotary column. A rotary column (hereinafter referred to as “column”) is housed and housed in a column container 5 that can be sealed so that its rotation can be adjusted. Although a mechanism for rotating the column is not shown here, as the mechanism, as the mechanism, the hollow shaft 3 is mounted on the column container 5 and the driving means is connected thereto, or the outer peripheral porous member 2 A part of them may be carried in the column container 5 by rollers or the like, and the driving means may be connected to the outer peripheral porous member.

As the outer peripheral porous member and the inner peripheral porous member, the ion exchange resin cannot pass through, but the liquid is a member having a large number of pores of a size that allows easy passage, and usually the ion exchange resin has a diameter of 0.2 to 2 mm. Considering that, for example, 74
It is like arranging holes with a diameter of about 1410 μm in a staggered pattern. For simplicity, a mesh member can be used.
It can be composed of a mesh of about 0 to 20 mesh. As the material, stainless steel or the like can be used, and the thickness may be enough to withstand the pressure applied during the ion exchange treatment. Specifically, the skeleton of the rotary column may be made of a structural material, and an outer peripheral or inner peripheral porous member may be stretched on the frame, or if the structural material itself has strength, It may be processed into a porous material to form a rotary column. The ion exchange processing chamber 6 is composed of the above-mentioned outer peripheral and inner peripheral porous members and a flat plate 7 that closes both peripheral ends of both members. The flat plate is not particularly limited as long as it constitutes a space.

The hollow shaft has a liquid supply / discharge orifice. The liquid is uniformly dispersed and supplied into the column through the orifice, and the liquid is discharged from the column. The size, shape, etc. of the orifice are not particularly limited and are set in consideration of the dispersion state with the liquid, the pressure loss and the like, but normally, several to several tens of those having a diameter of 1 to 5 mm may be appropriately provided.

Next, the sealable column container is provided with the hollow shaft and liquid supply / discharge pipes involved in the inflow / outflow of the liquid into the system. The pipe functions as a drain pipe when collecting the treatment liquid after the ion exchange treatment or collecting the regeneration liquid after the regeneration of the ion exchange resin. The column container can be hermetically sealed, and pressure can be applied to secure a constant flow of the liquid when forming the ion-exchange resin deposition layer or during the ion-exchange treatment.

Next, regarding the shape of the rotary column, the rotary column is cylindrical in FIG. 1, but the shape of the inner peripheral porous member is not particularly required to be cylindrical, and it may be cylindrical with a quadrangular cross section. Good. However, when the ion exchange resin deposition layer (hereinafter referred to as “body lamination”) is formed on the inner peripheral porous member,
The cylindrical shape is preferable from the viewpoint of uniformity of the deposited layer.

In the present invention, the relationship between the length of the rotary column (effective length of the ion exchange treatment chamber in the rotation axis direction) and the outer diameter is important for the efficiency of the ion exchange treatment in the present invention. That is, if the ion-exchange resin is dispersed and used in the ion-exchange treatment chamber, all the resins will be saturated in a short time, so it is important for the ion-exchange treatment to form a packed bed state. Is preferably relatively long along the direction of flow of
The outer diameter of the rotary column is preferably longer than its length. More preferably, the ratio of the outer diameter to the axial length is 3 or more. This makes it possible to form an efficient and effective deposition layer. Here, when the column is partitioned in the axial direction, the length in the rotation axis direction means that the uneven distribution of the ion-exchange resin in the axial direction is reduced and the packed bed is easily formed. Say. That is, when the column is integrated but is partitioned in the axial direction, not the column length but the length between partitions becomes the length in the rotation axis direction.

It is effective to divide the ion exchange treatment chamber into several chambers in order to form a uniform deposition layer without uneven distribution of the ion exchange resin in the circumferential direction of the column. By providing the partition plate, mutual variation can be prevented at least within the range partitioned by the partition plate. Therefore, the greater the number of partitioned rooms, the smaller the variation in the circumferential direction. The preferred number of rooms is about 4 to 6. Particularly, the partition plate is effective when the amount of ion exchange resin to be stored is relatively small. On the other hand, as the number of chambers increases, it takes more time to store the ion exchange resin in the column. If the partition plate is a perforated plate and the ion exchange resin can pass through relatively freely, even if there are variations at the beginning of storage, the ion exchange resin will be dispersed and uniform between the chambers after the rotary column is activated. Therefore, the problem of labor is reduced. Further, a partition plate may be an ordinary plate as long as each chamber is provided with a lid for accommodating an ion exchange resin and the same amount of resin is stored in each chamber in advance. However, it takes time to store. When a flat plate that is not a porous plate is used as the partition plate, the flow of the liquid does not occur in the circumferential direction in the column during the formation of the ion-exchange resin deposition layer, so that the deposition layer is easily formed. Here, the partition plate may be a partition plate that completely partitions the chamber or may have a vertical shape, which can prevent uneven distribution of the resin. In this case, the partition plate is attached to either the inner circumference or the outer circumference porous member depending on the position of the formed deposited layer, that is, the central portion or the outer peripheral portion.

Furthermore, in the present invention, in order to efficiently remove the air remaining in the column when the liquid is supplied into the column to the outside of the system, and to promote the destruction and dispersion of the deposited layer during the regeneration of the ion exchange resin, the amount of air is increased. A control mechanism may be provided. In particular, it is effective for regeneration efficiency to send air into the ion-exchange treatment chamber and promote agitation of the resin as the column rotates when the deposited layer is destroyed or dispersed. As a specific air amount control mechanism, for example, a pipe for air feeding may be connected to the hollow shaft and an air vent valve may be provided on the column container. Further, when the deposited layer is formed in the central portion of the column, the pipe for feeding air may be extended from the hollow shaft to the outer peripheral direction so as not to be buried in the deposited layer. On the other hand, when the deposited layer is formed on the outer peripheral portion of the column, the air feeding pipe does not need to extend from the hollow shaft in the outer peripheral direction.

Further, when actually configuring the ion exchanger using the column of the present invention, if necessary, various mechanisms based on known techniques such as various valves, pipes, sensors, drive motors, controllers, etc. are attached to the column or Just connect.

To actually use the rotary column ion exchanger of the present invention, it is better to use at least two units for the cation exchange resin and the anion exchange resin. In a normal ion exchange resin tower, since the specific gravities of the resins are different, there are many cases in which two layers are formed by utilizing this difference in specific gravities, that is, a mixed bed system is adopted. However, when the rotary column according to the present invention is used, it is difficult to form two layers. Therefore, as a general rule, it is advisable to use one layer, that is, multiple beds. That is, it is advisable to configure an ion exchange treatment device by serially connecting a rotation-resistant column ion exchanger containing a cation exchange resin and a rotary column ion exchanger containing an anion exchange resin.

Further, in order to systemize as an ion exchange device, at least two rotary columns are required as described above, but in consideration of continuous processing, it is advisable to use four as one set. In this case, if two units are used during the ion exchange process and the other two units are used during the regeneration process, it is possible to continuously perform desalting of whey or the like. The ion exchange resin that can be used in the present invention is not particularly limited, but the cation exchange resin has a styrene-divinylbenzene copolymer or the like as a base material and a sulfonic acid group, a carboxylic acid group or the like as a reactive group. As the anion exchange resin, a quaternary ammonium group based on a copolymer of styrene and divinylbenzene, etc.
It has a tertiary amine or the like as an exchange group, and usually has a diameter of about 0.2 to 3 mm and can be used regardless of the production method.

Next, the amount of the ion exchange resin stored in the column (that is, in the ion exchange treatment) is basically determined according to the thickness of the deposited layer for achieving the target ion exchange capacity. Although not limited, if the amount is too small, it becomes difficult to form a uniform deposited layer, and the efficiency of the ion exchange treatment becomes low. On the other hand, if the amount is too large, the fluidity in the column is lost and it becomes particularly difficult to regenerate the resin. As a preferable range, for effective deposition in the ion exchange treatment chamber,
It is good to store it so that it is about 30 to 70%.

Here, the main structural differences resulting from the difference in the mechanism of action between the rotary column containing the immobilized enzyme, which the present inventors previously applied, and the ion exchange resin-containing rotary column of the present application will be described.

First, it is assumed that the internal components are different, and as a problem before the structural difference, there is the fact that an effective ion exchange treatment cannot be carried out by simply using an ion exchange resin instead of the immobilized enzyme. This is because the formation of a deposited layer as a packing layer is essential in the ion exchange treatment, and it is not necessary to simply increase the contact efficiency, and the formation of the deposited layer is different from the case of using an immobilized enzyme. It is because a method is needed.

Next, the difference in structure will be described with respect to a preferred embodiment of the ion exchange treatment.

First, the column diameter-to-length ratio is defined to form an effective deposited layer. If the column length is longer than the diameter, it is difficult to uniformly form the resin deposition layer as the packing layer.

Second, since the diameter of the ion exchange resin is usually about 0.2 to 2 mm, the pores of the porous member must be suitable for this.

Thirdly, since the deposition layer formation is achieved by the relative relationship between the flow of the liquid and the rotation of the column, it is necessary to have a structure capable of applying a liquid pressure capable of optimizing the flow of the liquid.

Fourthly, the treatment is performed by passing the deposited layer, and in this sense, the treatment is continuous, and therefore, it is not necessary to provide a mechanism for retaining the liquid in the column to a certain extent, for example, an overflow mechanism. .

Next, a method of performing an ion exchange treatment using the ion exchanger of the present invention will be described. This method has two modes: a mode in which the liquid flow is from the outer circumference of the column to the center and a mode in which the liquid flow is from the center to the outer circumference. First, the aspect of outer circumference → center will be described.

The processing according to this aspect is roughly divided into three stages.

Deposited layer forming process: While rotating the rotary column, the ion exchange resin deposited layer forming liquid is supplied from the outer peripheral porous member side through the liquid supply / discharge pipes, and the inner peripheral porous member side through the hollow shaft. Then, the liquid is discharged to form an ion-exchange resin deposition layer on the inner peripheral porous member. A conceptual cross-sectional view of the formed deposited layer is shown in FIG. In this figure, an example of four chambers using four partition plates 9 is shown, and a hollow shaft, a column container, etc. are not shown. As described above, in this embodiment, the sedimentary layer 8 is formed near the center of the column (actually, the shape is slightly influenced by the centrifugal force and depends on the rotation direction.) Here, the sedimentary layer is formed near the center of the rotary column ( The mechanical relationship for forming on the inner peripheral porous member) will be described.
In this embodiment, since the sedimentary layer is formed against centrifugal acceleration and gravitational acceleration, a liquid flow corresponding to it from the outer circumference to the center is required. The mechanical relationship is not a problem as long as the deposited layer is formed, but a concrete indication of the rotation speed is that the final velocity of the ion-exchange resin toward the outer periphery of the rotary column at the bottom of the column is the flow velocity of the liquid flowing in the rotary column. It can be defined as a speed that is smaller than that (hereinafter, referred to as "low speed 1").

Here, the speed at which the terminal velocity of the ion exchange resin (hereinafter referred to as "resin") toward the column outer periphery is smaller than the flow velocity of the liquid flowing in the rotary column is the acceleration of the resin acting in the column outer periphery direction. (The maximum acceleration is from the center where gravity acceleration and centrifugal acceleration overlap at the lower part of the column to the outer periphery, and the terminal velocity of the resin at this position should be smaller than the flow velocity.) This is the condition for depositing. The terminal velocity can be estimated by the following general terminal velocity relational expression due to sedimentation of particles.

When Re <2, U = a (ρs−ρf) D ² / 18μ 2 <Re <500, U = [(4/225) (ρs−ρf) a ² / (μρf] ^1/3 D 500 <Re <10 ^{In 5} , U = √3a (ρs−ρf) D / ρf (where Re: Reynolds number, U: terminal velocity, a: gravitational acceleration + centrifugal acceleration on the surface of the sediment layer, ρs: resin density,
ρf: density of liquid, D: diameter of resin, μ: viscosity of liquid. ) In the above equation, the Re number is defined as Re = DUρf / μ, and therefore the applicable equation can be determined in relation to the calculated U.

A deposition layer can be formed by making the flow velocity of the liquid toward the center of the column larger than the value of U calculated above.
Therefore, in the flow of this embodiment, the flow rate increases as the number of revolutions increases, and the liquid supply pressure also increases, which may cause problems in ion exchange treatment efficiency, device structure, and operation. The appropriate number of revolutions may be appropriately set in consideration of the size of the resin, the thickness of the deposited layer, the necessary ion exchange capacity, etc., depending on the mechanical relationship required for forming the deposited layer, but the preferred range is 1 to
It is 50 rpm, more preferably 5 to 20 rpm. This is for a column diameter of about 20 to ²⁰⁰ cm, which corresponds to a centrifugal acceleration of about 0.001 to 27.4 m / s ² . If too late,
A channeling flow that tends to occur in a normal packed bed type is likely to occur.

The ion exchange resin deposited layer forming liquid may be water or a liquid to be treated. That is, the ion exchange treatment is insufficient until the formation of the deposited layer, but the time required for the formation of the deposited layer is short considering the total processing time (generally about 2 to 3 hours). The liquid itself may be used, or the liquid to be treated used for forming the deposited layer may be separately collected and appropriately treated depending on whether it flows in at the time of the next treatment or a partial circulation system is used. A liquid that does not directly affect the ion exchange treatment, such as water, may be used, and it is preferable to use water because it can prevent the resin from being saturated immediately. In this case, it is sufficient to switch to the liquid to be treated after the deposited layer is formed. Whether or not the deposited layer has been formed can be known from the change in pressure loss during liquid supply, and therefore the deposited layer formation → ion exchange treatment can be continuously performed as a series of operations.

In the method according to this embodiment, the specific gravity of the resin is preferably relatively light, and is preferably 1.3 or less, particularly 1.2 or less, because the deposition layer is formed in relation to the terminal velocity of the resin and the liquid flow. However, if the apparent specific gravity is lighter than the specific gravity of the liquid, sedimentation does not occur in the first place, so it is difficult to target too light ones, but after swelling, the ion exchange resin is usually heavier than the liquid, so in most cases the lower limit of It can be said that there is no limit. As a resin with a specific gravity of 1.2 or less, DIAION (PK208, PA30
6, WK10), chitopearl and the like.

Ion exchange treatment step: The rotation type column is continuously rotated, the liquid to be treated is supplied from the liquid supply / discharge pipes, passed through the deposition layer, and discharged from the hollow shaft to perform the ion exchange treatment.

In order to obtain a processing liquid having a desired pH and electric conductivity,
The rotation speed related to the flow rate of the liquid to be treated and the flow velocity in the deposited layer may be controlled. In principle, the rotation speed may be the low speed 1, but it may be adjusted in consideration of the above relationship.

The ion-exchange treatment liquid may be collected after the deposited layer is formed and stabilized. If the deposition layer cannot be retained unless the flow rate is increased to some extent, the ion exchange treatment may not be sufficiently performed, so a circulation system in which the recovery liquid is partially circulated may be adopted.

Whether the resin's ion exchange capacity is approaching saturation
Since it can be known from changes in pH, changes in electrical conductivity, etc., these detectors may be installed at the outlet of the processing liquid.

Resin regeneration process: The treatment liquid is recovered, and then the liquid for ion exchange regeneration is supplied into the rotary column through the hollow shaft, and the rotary column is rotated at a speed higher than the low speed 1 (high speed 1) at the same time. By doing so, the deposited layer is destroyed and dispersed.

After finishing the treatment, drain the treatment liquid remaining in the column,
Depending on the intended treatment liquid, this may be mixed with the recovered treatment liquid, or may be treated separately as the ion exchange treatment is insufficient and treated at the next treatment.

In a normal packed bed type ion exchange resin tower, the resin layer must be forcibly agitated manually, but in this rotary column, hot water, regeneration liquid, etc. However, by rotating the column at a high speed, the accumulated layer is destroyed and dispersed, whereby the regeneration of the resin can be greatly simplified.

Here, the liquid for ion exchange regeneration includes all liquids relating to regeneration, and also includes hot water or water used for destroying the deposited layer, a regenerating liquid used for regeneration, and water for washing with water. The regenerant may be a commonly used one, for example, a 3 to 4% HCl solution or the like may be used for the cation exchange resin and a 3 to 4% NaOH solution or the like may be used for the anion exchange resin.

At the time of destruction of the deposited layer, it is advisable to use the above-mentioned air amount control mechanism to introduce air of about 10 to 30% of the volume of the ion exchange treatment chamber into the column to promote the stirring of the resin. Since air or a liquid for regeneration is supplied into the column and the column rotates at high speed, the destruction and dispersion of the deposited layer formed near the center of the column is dramatically improved.

Here, the high speed 1 is a speed higher than the low speed 1, and is a speed that can impart a centrifugal acceleration that can sufficiently destroy the deposited layer, and may be a speed at which the resin after dispersion is not consolidated. It is preferably 20 to 400 rpm, particularly about 50 to 200 rpm (with a column diameter of 20 to 200 cm). The centrifugal acceleration may be about 27 to 440 m / s ² .

The regeneration treatment is completed by washing the resin with water. It is possible to continuously shift from the ion exchange treatment to the regeneration treatment by switching the supply liquid, and after the washing with water, it is possible to shift to the step of forming the deposited layer again. Continuous processing is feasible.

According to this aspect, channeling is particularly unlikely to occur, and
The resin is less likely to be consolidated, the efficiency of the ion exchange treatment can be improved, and the centrifugal force can be effectively used to destroy the deposited layer, so that the regeneration treatment becomes extremely easy.

Next, another mode in which the deposited layer is formed on the outer peripheral side will be described. The processing according to this aspect is also divided into three stages as described above. The parts not specifically mentioned are the same as those in the above embodiment.

Deposited layer forming step: While rotating the rotary column, the ion exchange resin deposited layer forming liquid is supplied from the inner peripheral porous member side through the hollow shaft, and the liquid is supplied and discharged from the outer peripheral porous member side, if necessary. By discharging the liquid through a pipe, an ion exchange resin deposition layer is formed on the outer peripheral porous member. A conceptual diagram of the formed deposited layer is shown in FIG. In this figure, the partition plate 9
An example of 4 chambers using 4 sheets is shown, and a hollow shaft, a column container, etc. are not shown. As described above, in this embodiment, the deposition layer 8 is formed in the outer circumference of the column (actually, the shape is changed depending on the rotation direction due to the influence of the centrifugal force). The mechanical relationship for forming the layer) is relatively simple as compared with the above-described embodiment because the sedimentary layer has the same centrifugal acceleration and the direction of the liquid flow, and the liquid flow is not an essential factor for forming the sedimentary layer. That is, if the centrifugal acceleration exceeds the gravitational acceleration over the entire column, the liquid flow is not necessary. However, if the column rotation speed is defined from the mechanical relationship including the liquid flow, the rotation type column of the ion exchange resin It can be said that the terminal velocity toward the center is smaller than the flow velocity of the liquid flowing in the rotary column (hereinafter referred to as "high speed 2"). The above relationship may not be specified as long as the deposited layer is formed, but it can be used as a measure of speed in practical use. However, particularly in this embodiment, since the resin tends to adhere to the outer peripheral porous member and the resin due to swelling,
Even if the centrifugal acceleration is smaller than the calculated value, the resin does not fall and a deposited layer can be formed. The influence of adhesion varies depending on the individual case and cannot be specified unconditionally. Therefore, it should be properly incorporated into the design during actual process design.

Here, the concept of terminal speed etc. is the same as in the above case,
In this embodiment, the problem is the terminal velocity from the outer circumference to the center, and in reality, the direction of gravity acceleration and the direction of centrifugal acceleration are overlapped and face toward the center from the uppermost column. This terminal velocity should be smaller than the liquid flow velocity flowing from the center of the column to the outer periphery, and in this case, the resin moves and accumulates along the liquid flow to the outer periphery of the column. Therefore, a in the above calculation formula is a value of approximately [a: gravitational acceleration-centrifugal acceleration applied to the surface of the deposited layer] unless the adhesiveness of the resin is taken into consideration. If the centrifugal acceleration is sufficiently large, the terminal velocity will be negative, that is, the resin will go from the center toward the outer circumference, and can be deposited on the outer circumference side even if there is no liquid flow. Therefore,
In the dynamic relation of this embodiment, the liquid flow is not an essential requirement for forming the deposited layer.

That is, in this aspect, since the liquid flow and the centrifugal acceleration directionality are the same, their influence on the formation of the deposited layer is small. Therefore, it is meaningless to use a small centrifugal acceleration, and it is preferable to improve the efficiency of forming the deposited layer at a relatively high speed. However, if the speed is too high, the resin may be consolidated. 20 to 400 rpm as a preferable rotation speed, especially 50 to 20
It is about 0 rpm (assuming that the column diameter is about 20 to 200 cm).

The main difference between the above embodiment and this embodiment is due to the specific gravity of the resin. That is, when the specific gravity of the ion exchange resin is large and it is difficult to balance the flow velocity and the behavior of the ion exchange resin, that is, when the specific gravity is larger than 1.1, especially 1.2, the column is rotated after storing the ion exchange resin and dispersed evenly in each chamber. After letting
It is preferable that the column is rotated at a high speed to form a deposited layer of the ion exchange resin inside the outer peripheral portion of the column, and then whey or the like is passed from the central portion of the column to the outer peripheral side of the column. In the above, it is preferable to have a partition plate. This is because it is difficult to balance the flow velocity, the centrifugal movement and the resin behavior, and the resin is likely to be unevenly distributed in the column (ion exchange treatment chamber). On the other hand, in this embodiment, since the ion exchange treatment is also performed at a high speed, and since the liquid flow is directed from the center to the outer periphery, a circumferential flow due to rotation is likely to occur. Since a steady flow in the radial direction is important in forming the deposited layer, it is preferable to suppress the flow in the circumferential direction as much as possible.
Therefore, as the partition plate used in this embodiment, it is better to use a flat plate having no holes instead of a perforated plate. As a resin with a specific gravity greater than 1.2, DIAION (PK216, PK220, PK22
8) etc. can be illustrated.

Ion exchange treatment step: The ion exchange treatment is performed by continuing rotation of the rotary column, supplying the liquid to be treated from the hollow shaft, passing through the deposited layer, and further discharging.

In order to obtain a processing liquid having a desired pH and electric conductivity,
The rotation speed related to the flow rate of the liquid to be treated and the flow velocity in the deposited layer may be controlled. In principle, the rotation speed may be high speed 2, but it may be adjusted in consideration of the above relationship.

In this aspect, since the centrifugal force is effectively used,
Further, since the liquid flows from the center to the outer periphery, the pressure loss of the liquid supply can be small. Furthermore, in this embodiment, the speed of the liquid to be processed passing through the deposition layer can be adjusted by the number of rotations of the column in addition to the flow rate supplied, and the width of the control means for the ion exchange processing efficiency is wide, The top is convenient.

Resin regeneration process: The treated liquid is recovered, and then the liquid for ion exchange regeneration is supplied into the rotary column through the liquid supply / discharge pipes, and at the same time, the rotary column is fed at a speed lower than high speed 2 ( "Low speed 2"
Say. ) To destroy the deposited layer,
Disperse.

Here, in a normal packed bed type ion exchange resin tower, the resin layer must be forcibly stirred by hand, but in this rotary column, hot water, regeneration liquid, etc. are passed from the outer peripheral side of the column. While rotating the column at low speed, the ion exchange resin is dropped and dispersed by the flow of the liquid and its own weight. In this way, it is extremely easy to disperse the resin when regenerating the ion exchange resin.

Further, at this time, similarly to the above-described aspect, it is possible to promote the destruction and dispersion of the deposited layer by introducing air into the column by using the air amount control mechanism.

In this embodiment, the low speed 2 is a speed slower than the high speed 2, and may be a speed at which the deposited layer can drop due to its own weight and at which resin can be agitated, but preferably 1 to 50 rpm. Especially, it is about 5 to 20 rpm.

Also in this embodiment, the deposition layer formation → ion exchange treatment → regeneration treatment can be carried out by a series of operations, and can further be continuously repeated.

In the two methods described above, the liquid to be treated that can be treated includes whey for desalting, skim milk,
Examples of the water include water, but not limited to these.
Any liquid that can be subjected to an ion exchange treatment can be the subject of the present invention.

〔Example〕

 Examples will be shown below and further described.

Example 1 The rotation type column shown in FIG. 1 is divided into four chambers by four partition plates (flat plate without holes), and the outer peripheral porous member of each chamber is provided with a lid for resin storage. Type column (capacity 600ml, diameter to length ratio 3.6) cation exchange resin IR-12
0B (specific gravity 1.24, average diameter 0.45 to 0.60 mm, Organo Corporation)
400 ml (corresponding to a layer height of 27 mm) was evenly added. Metal mesh (200 mesh) as the outer and inner porous members
Was used.

This column was rotated at 150 rpm, and a deposited layer of ion exchange resin was formed inside the outer peripheral portion of the column by centrifugal force. And while maintaining rotation, whey (pH 6.14,
Cation exchange treatment was performed while passing an electric conductivity of 5.01 mS / cm) at a flow rate of 2.1 / hr, and another anion exchange resin (IRA-400, 435 ml, continuously formed in the same manner) was used.
The specific gravity was 1.22, the average diameter was 0.41 to 0.48 mm, and the bed height was 30.2 mm. The pH change of the whey thus treated was about 1 to 3 after the cation exchange, and as shown in FIG. 4 after the anion exchange. The pH of the treatment liquid decreased with time, and the decrease particularly after 30 minutes was extremely rapid (this means that the resin has reached saturation). Then, when the solution was passed until it reached pH 6, the time was about 90 minutes, the throughput was 3.15,
Ions could be exchanged efficiently. The electrical conductivity is
It was 1.94 mS / cm.

In the examples, the liquid was not supplied when the deposited layer was formed, but the mechanical relationship in the column was as follows.

・ Centrifugal acceleration on the surface of sedimentary layer = ω ² × r = (150/60 × 2π) ² × (145 / 2-27) × 10 ^-3 = 11.2m / s ²・ Acceleration from the top of the column to the center a = 9.8 −11.2 = −1.4 m / s ²・ Applicable formula: Formula corresponding to the above 2 <Re <500 ・ Terminal velocity U = −0.9 × 10.3 ^-3 m / s Therefore, since the acceleration a is negative, the final velocity is Since it becomes negative, it can be seen that the deposited layer is sufficiently formed without the liquid flow.

Next, these resins were regenerated. The column was rotated at 10 rpm while passing hot water from the outer peripheral side of each column, and the resin was dropped and dispersed in the column by its flow and the own weight of the resin. In this case, the resin dispersed instantly. Further, after passing hot water to wash the waste liquid until it becomes clean, 3-4% HCl is passed through the cation exchange resin side, and 3-4% NaOH is passed through the anion side. And played it back. Thus, the regeneration process was extremely easy.

〔The invention's effect〕

As described above, by performing the ion exchange treatment with the rotary column, the packed bed of the resin is formed → the ion exchange treatment →
It becomes possible to perform the playback process as a series of operations,
Further, since this operation can be repeatedly performed, the ion exchange treatment can be made continuous. In particular, the regenerating process of the resin is remarkably simplified as compared with the conventional case where the filling layer is broken and labor is required manually. Further, more appropriate treatment can be realized by appropriately selecting the treatment method having two modes depending on the type of the ion exchange resin used. The ion exchanger of the present invention is used for anion exchange and cation exchange.
If you connect the units, you can easily configure the ion exchange processing device,
The present invention is a very useful technique for ion exchange treatment.

[Brief description of drawings]

FIG. 1 is a schematic perspective view showing an example of the rotary column ion exchanger of the present invention, FIG. 2 is a conceptual cross-sectional view of a column in a mode in which a deposited layer is formed near the center of the column, and FIG. 3 is a deposited layer. Is a conceptual cross-sectional view of the column in a mode in which is formed on the outer circumference of the column, and FIG. 4 is a graph showing the change with time of pH of the treatment liquid obtained in the example. 1 ... Inner peripheral porous member 2 ... Outer peripheral porous member 3 ... Hollow shaft 4 ... Liquid supply / discharge pipe 5 ... Column container 6 ... Ion exchange treatment chamber 7 ... Flat plate 8 ... Deposition Layer 9: Partition plate 10: Air vent

Claims (13)

[Claims] 1. An ion-exchange resin is housed in an ion-exchange treatment chamber sandwiched between an outer peripheral porous member and an inner peripheral porous member, and the ion-exchange treatment chamber has a peripheral diameter longer than the length in the rotation axis direction. Then, a rotary type column comprising a hollow shaft having a liquid supply / discharge orifice in the rotary shaft portion, and a rotary type column internally rotatably adjustable and equipped with a liquid supply / discharge pipe, which can be hermetically sealed. Rotary column ion exchanger with a built-in ion exchange resin that is composed of at least a column container. 2. The rotary column ion exchanger according to claim 1, wherein the ion exchange treatment chamber is divided into a plurality of chambers by a partition plate. 3. The rotary column ion exchanger according to claim 1, further comprising an air amount control mechanism for introducing air into the ion exchange processing chamber. 4. The rotary column ion exchanger according to claim 1, wherein the peripheral diameter of the rotary column is three times or more the length in the direction of the rotary shaft. 5. A rotary column ion exchanger according to claim 1, which contains a cation exchange resin, and a rotary column ion exchanger according to claim 1, which contains an anion exchange resin, connected in series. Ion exchange treatment equipment. 6. An ion exchange treatment method comprising the following steps carried out using the ion exchange resin built-in rotary column ion exchanger according to claim 1. Step: While rotating the rotary column, the ion exchange resin deposition layer forming liquid is supplied from the outer peripheral porous member side through the liquid supply / discharge pipe, and the inner peripheral porous member side is supplied through the hollow shaft. By discharging the liquid, an ion exchange resin deposition layer is formed on the inner peripheral porous member. Step: The ion exchange treatment is carried out by continuing the rotation of the rotary column, supplying the liquid to be treated from the liquid supply / discharge pipes, passing it through the deposition layer, and discharging it from the hollow shaft. Step: recovering the treatment liquid, then supplying the liquid for ion exchange regeneration into the rotary column through the hollow shaft, and at the same time, rotating the rotary column at a higher speed to destroy the deposited layer, Disperse. 7. The rotation speed of the rotary column in the step is such that the terminal speed of the ion exchange resin from the center of the column toward the outer circumference is smaller than the flow speed of the liquid flowing in the column. The ion exchange treatment method described. 8. The ion exchange treatment method according to claim 7, wherein the specific gravity of the ion exchange resin is 1.2 or less. 9. The ion exchange treatment method according to claim 7, wherein the rotation speed of the rotary column is in the range of 1 to 50 rpm in the steps and 20 to 400 rpm in the steps. 10. An ion exchange treatment method comprising the following steps performed using the rotary column ion exchanger with a built-in ion exchange resin according to claim 1. Process: While rotating the rotary column, the ion exchange resin deposition layer forming liquid is supplied from the inner peripheral porous member side via the hollow shaft, and the outer peripheral porous member side via the liquid supply / discharge pipes as necessary. Then, the liquid is discharged to form an ion exchange resin deposition layer on the outer peripheral porous member. Step: The ion exchange treatment is performed by continuing the rotation of the rotary column, supplying the liquid to be treated from the hollow shaft, passing it through the deposition layer, and discharging it from the liquid supply / discharge pipe. Step: recovering the treatment liquid, and then supplying a liquid for ion exchange regeneration into the rotary column through a liquid supply / discharge pipe, and at the same time rotating the rotary column at a slower speed Destroy and disperse the deposited layer. 11. The rotating speed of the rotary column in the step is such that the terminal speed of the ion exchange resin from the outer circumference of the column toward the center is smaller than the flow speed of the liquid flowing in the column. The ion exchange treatment method described. 12. The ion exchange treatment method according to claim 10, wherein the specific gravity of the ion exchange resin is larger than 1.2. 13. The ion exchange treatment method according to claim 10, wherein the rotation speed of the rotary column is in the range of 20 to 400 rpm in the step and in the range of 1 to 50 rpm in the step.