阅读说明：本技术 离子交换树脂的预处理装置和离子交换树脂的预处理方法 (Pretreatment device and pretreatment method for ion exchange resin ) 是由 合庭健太 中村彰 于 2019-09-27 设计创作，主要内容包括：本发明提供一种可简便且经济地降低含水量的离子交换树脂的预处理装置。一种离子交换树脂的预处理装置,其特征在于,其至少具有：原液罐,其储存非水溶剂；离子交换树脂容器,其收纳有离子交换树脂；水分除去装置,其除去非水溶剂中的水分,并且,上述离子交换树脂的预处理装置具有选自以下的至少一个送液管：从上述原液罐开始,按照上述离子交换树脂容器和上述水分除去装置的顺序通入非水溶剂后,将通入的非水溶剂送回至上述原液罐的循环送液管；以及从上述原液罐开始,按照上述水分除去装置和上述离子交换树脂容器的顺序通入非水溶剂后,将通入的非水溶剂送回至上述原液罐的循环送液管。(The invention provides a pretreatment device for ion exchange resin, which can simply and economically reduce the water content. An apparatus for pretreating an ion exchange resin, comprising at least: a raw liquid tank storing a nonaqueous solvent; an ion exchange resin container that contains an ion exchange resin; a water removal device for removing water in a nonaqueous solvent, wherein the pretreatment device for an ion exchange resin has at least one liquid delivery tube selected from the group consisting of: a circulating liquid feed pipe for feeding back a nonaqueous solvent introduced from the raw liquid tank to the raw liquid tank after introducing the nonaqueous solvent into the ion exchange resin container and the moisture removal device in this order; and a circulation liquid feed pipe for feeding back the introduced nonaqueous solvent to the raw liquid tank after introducing the nonaqueous solvent from the raw liquid tank in the order of the moisture removal device and the ion exchange resin container.)

1. An apparatus for pretreating an ion exchange resin, comprising at least:

a raw liquid tank storing a nonaqueous solvent;

an ion exchange resin container that contains an ion exchange resin; and

a moisture removing device which removes moisture in the non-aqueous solvent and,

the pretreatment device for ion exchange resin has at least one liquid sending pipe selected from the group consisting of:

a circulating liquid feeding pipe for feeding back the introduced nonaqueous solvent to the raw liquid tank after introducing the nonaqueous solvent from the raw liquid tank in the order of the ion exchange resin container and the moisture removing device; and

and a circulating liquid feed pipe for returning the introduced nonaqueous solvent to the raw liquid tank after introducing the nonaqueous solvent from the raw liquid tank in the order of the moisture removal device and the ion exchange resin container.

2. The apparatus for pretreating ion exchange resin according to claim 1,

the moisture removing device is a moisture adsorbing device.

3. The apparatus for pretreating ion exchange resin according to claim 2,

the moisture adsorption device contains zeolite as a moisture adsorption material.

4. The apparatus for pretreating ion exchange resin according to claim 3,

the circulating liquid sending pipe is configured as follows: the nonaqueous solvent flowing through the circulating liquid feeding pipe is introduced so as to flow upward with respect to the zeolite contained in the moisture adsorbing device.

5. The apparatus for pretreating ion exchange resin according to any one of claims 1 to 4, wherein,

the downstream side of the moisture removing device is also provided with a filtering device.

6. The apparatus for pretreating ion exchange resin according to any one of claims 1 to 5, wherein,

the ion exchange resin is an anion exchange resin.

7. The apparatus for pretreating ion exchange resin according to any one of claims 1 to 6, wherein,

the ion exchange resin is a weak-base anion exchange resin.

8. A method for pretreating an ion exchange resin,

the pretreatment apparatus for an ion exchange resin is fed while circulating a nonaqueous solvent,

the pretreatment device for ion exchange resin at least comprises:

a raw liquid tank storing a nonaqueous solvent;

an ion exchange resin container that contains an ion exchange resin; and

a water removing device for removing water in the non-aqueous solvent,

the liquid delivery is selected from one or more of the following:

a liquid feed step of feeding back the introduced nonaqueous solvent to the raw liquid tank after introducing the nonaqueous solvent from the raw liquid tank in the order of the ion exchange resin container and the moisture removal device, and

and a liquid feed step of feeding back the introduced nonaqueous solvent to the raw liquid tank after introducing the nonaqueous solvent from the raw liquid tank in the order of the moisture removal device and the ion exchange resin container.

Technical Field

The present invention relates to an apparatus and a method for pretreating an ion exchange resin.

Background

In recent years, nonaqueous solvents that are highly purified from impurities have been used as semiconductor manufacturing processes, electrolytes for lithium ion batteries, and the like.

As a method for purifying a nonaqueous solvent, a distillation method for removing impurities by distillation is known, but there are technical problems that a large burden is imposed on equipment cost, a large amount of energy is required for a distillation treatment, and high purification is difficult.

Therefore, in recent years, a method of purifying a nonaqueous solvent by an ion exchange method using an ion exchange resin or an ion exchange filter has been proposed. According to the ion exchange method, the burden of equipment cost is small, energy is saved, and impurities are removed by high purification.

For example, an electrolyte solution for a lithium ion battery is produced by dissolving an electrolyte such as a fluorine-based lithium salt in a nonaqueous solvent.

Since acids (mainly hydrogen fluoride) are impurities in the electrolyte solution, a purification method for removing them by an ion exchange resin has been studied, but since water also becomes impurities at the same time, a pretreatment for reducing the water content of the ion exchange resin is required so that the water content of the ion exchange resin does not dissolve out in the electrolyte solution.

As a method for reducing the moisture content of the ion exchange resin, a method of drying the ion exchange resin under reduced pressure, a method of drying under reduced pressure and removing the nonaqueous solvent by passing the nonaqueous solvent through the ion exchange resin are known (for example, see patent document 1 (japanese patent application laid-open No. 2000-505042)).

Documents of the prior art

Patent document

Patent document 1: japanese Kohyo publication 2000-505042

Disclosure of Invention

Problems to be solved by the invention

However, the present inventors have conducted studies and, as a result, have found that: the reduced-pressure drying cannot sufficiently reduce the water content of the ion exchange resin, and even in the case of the method in which the non-aqueous solvent is introduced after drying under reduced pressure, a large amount of the non-aqueous solvent is required in an amount several tens to several hundreds times the amount of the ion exchange resin.

In view of the above situation, an object of the present invention is to provide an apparatus and a method for pretreating an ion exchange resin, in which the water content can be reduced easily and economically.

The present inventors have made extensive studies to achieve the above object, and as a result, have found that: the above technical object can be achieved by an ion exchange resin pretreatment apparatus comprising at least: a raw liquid tank storing a nonaqueous solvent; an ion exchange resin container that contains an ion exchange resin; and a water removal device for removing water in the nonaqueous solvent, wherein the pretreatment device for the ion exchange resin has at least one liquid delivery tube selected from the group consisting of: a circulating liquid feed pipe for feeding back the introduced nonaqueous solvent to the raw liquid tank after introducing the nonaqueous solvent from the raw liquid tank in the order of the ion exchange resin container and the moisture removal device; the present invention has been completed based on the finding that a nonaqueous solvent is introduced into the raw liquid tank in this order from the water removal device to the ion exchange resin container, and then the introduced nonaqueous solvent is returned to the circulation feed pipe of the raw liquid tank.

Namely, the present invention provides the following.

(1) An apparatus for pretreating an ion exchange resin, comprising at least:

a raw liquid tank storing a nonaqueous solvent;

an ion exchange resin container that contains an ion exchange resin; and

a moisture removing device which removes moisture in the non-aqueous solvent and,

the pretreatment device for ion exchange resin has at least one liquid sending pipe selected from the group consisting of:

a circulating liquid feed pipe for feeding back a nonaqueous solvent introduced from the raw liquid tank to the raw liquid tank after introducing the nonaqueous solvent into the ion exchange resin container and the moisture removal device in this order; and

after introducing a nonaqueous solvent from the raw liquid tank in the order of the moisture removal device and the ion exchange resin container, the introduced nonaqueous solvent is returned to the circulation liquid-feeding pipe of the raw liquid tank.

(2) The apparatus for pretreating an ion exchange resin according to item (1), wherein the moisture removing device is a moisture adsorbing device.

(3) The pretreatment apparatus for an ion exchange resin according to the above (2), wherein the moisture adsorption device contains zeolite as a moisture adsorbent.

(4) The apparatus for pretreating an ion exchange resin according to item (3) above, wherein,

the circulating liquid delivery pipe is configured as follows: the nonaqueous solvent flowing through the circulating liquid feeding pipe is introduced so as to flow upward with respect to the zeolite contained in the moisture adsorbing device.

(5) The apparatus for pretreating an ion exchange resin according to any one of (1) to (4), wherein a filtration device is further provided downstream of the moisture removal device.

(6) The apparatus for pretreating an ion exchange resin according to any one of (1) to (5), wherein the ion exchange resin is an anion exchange resin.

(7) The apparatus for pretreating an ion exchange resin according to any one of (1) to (6), wherein the ion exchange resin is a weakly basic anion exchange resin.

(8) A method for pretreating an ion exchange resin,

the pretreatment apparatus for an ion exchange resin is fed while circulating a nonaqueous solvent,

the pretreatment unit for the ion exchange resin at least comprises:

a raw liquid tank storing a nonaqueous solvent;

an ion exchange resin container that contains an ion exchange resin; and

a water removing device for removing water in the non-aqueous solvent,

the liquid delivery is selected from one or more of the following:

introducing a nonaqueous solvent into the raw liquid tank in this order from the ion exchange resin container to the moisture removal device, and then returning the introduced nonaqueous solvent to the raw liquid tank, and

and a liquid feed step of feeding back the introduced nonaqueous solvent to the raw liquid tank after introducing the nonaqueous solvent from the raw liquid tank in the order of the moisture removal device and the ion exchange resin container.

Effects of the invention

According to the present invention, an apparatus for pretreating an ion exchange resin and a method for pretreating an ion exchange resin can be provided, in which the water content can be reduced simply and economically.

Drawings

FIG. 1 is a diagram for explaining the structure of an apparatus for pretreating an ion exchange resin according to the present invention.

FIG. 2 is a view showing an example of the form of an apparatus for pretreating an ion exchange resin according to the present invention.

FIG. 3 is a view showing an example of the form of an apparatus for pretreating an ion exchange resin according to the present invention.

FIG. 4 is a view showing an example of the form of an apparatus for pretreating an ion exchange resin according to the present invention.

FIG. 5 is a view showing the form of an apparatus for pretreating an ion exchange resin in a comparative example of the present invention.

Detailed Description

The pretreatment device for an ion exchange resin according to the present invention is characterized by comprising at least: a raw liquid tank storing a nonaqueous solvent; an ion exchange resin container that contains an ion exchange resin; and a water removal device for removing water in the nonaqueous solvent, wherein the pretreatment device for the ion exchange resin has at least one liquid delivery tube selected from the group consisting of: a circulating liquid feed pipe for feeding back a nonaqueous solvent introduced from the raw liquid tank to the raw liquid tank after introducing the nonaqueous solvent into the ion exchange resin container and the moisture removal device in this order; and a circulation liquid feed pipe for feeding back the introduced nonaqueous solvent to the raw liquid tank after introducing the nonaqueous solvent from the raw liquid tank in the order of the moisture removal device and the ion exchange resin container.

Hereinafter, an apparatus for pretreating an ion exchange resin according to the present invention will be described with reference to the accompanying drawings.

FIG. 1 is a diagram showing a configuration example of an ion exchange resin pretreatment apparatus according to the present invention.

As shown in fig. 1 (a) to 1 (c), the ion exchange resin pretreatment device 1 according to the present invention includes at least a raw liquid tank 2 for storing a nonaqueous solvent, an ion exchange resin container 3 for housing an ion exchange resin, and a water removal device 4 for removing water in the nonaqueous solvent.

The pretreatment device for an ion exchange resin according to the present invention has a circulation liquid feed pipe for feeding back a nonaqueous solvent fed from a raw liquid tank to the raw liquid tank.

The pretreatment device 1 for an ion exchange resin according to the present invention has a liquid sending tube selected from at least one of the following: a circulation feed pipe L for feeding back the introduced nonaqueous solvent to the raw liquid tank 2 after introducing the nonaqueous solvent from the raw liquid tank 2 in the order of the ion exchange resin container 3 and the moisture removal device 4 as exemplified in FIG. 1 (a), and a circulation feed pipe L for feeding back the introduced nonaqueous solvent to the raw liquid tank 2 after introducing the nonaqueous solvent from the raw liquid tank 2 in the order of the moisture removal device 4 and the ion exchange resin container 3 as exemplified in FIG. 1 (b).

As illustrated in fig. 1 (c), the ion exchange resin pretreatment device 1 according to the present invention may include: a circulating liquid feeding pipe L1 for feeding back the introduced nonaqueous solvent to the raw liquid tank 2 after introducing the nonaqueous solvent in the order of the ion exchange resin container 3 and the moisture removal device 4 from the raw liquid tank 2, and a circulating liquid feeding pipe L2 for feeding back the introduced nonaqueous solvent to the raw liquid tank 2 after introducing the nonaqueous solvent in the order of the moisture removal device 4 and the ion exchange resin container 3 from the raw liquid tank 2.

In the embodiment illustrated in fig. 1 (c), when the nonaqueous solvent is introduced, the valve of the liquid sending tube provided in either one of the circulation liquid sending tube L1 and the circulation liquid sending tube L2 is closed, and the nonaqueous solvent is introduced into the other liquid sending tube.

In the pretreatment apparatus for an ion exchange resin according to the present invention, the nonaqueous solvent includes an organic nonaqueous solvent.

The nonaqueous solvent is preferably the same as the nonaqueous solvent that flows through the ion exchange resin after the pretreatment by the ion exchange resin pretreatment apparatus according to the present invention.

Examples of the organic nonaqueous solvent include solvents selected from methanol, ethanol, N-propanol, Isopropanol (IPA), t-butanol, ethylene glycol, diethylene glycol, glycerol, N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), Propylene Glycol Monomethyl Ether (PGME), Propylene Glycol Monomethyl Ether Acetate (PGMEA), butyl carbitol (BDG), Monoethanolamine (MEA), methyl lactate, ethyl acetate, butyl acetate, isoamyl acetate, acetone, Methyl Ethyl Ketone (MEK), methyl isobutyl ketone (MIBK), toluene, xylene, cyclohexane, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, γ -butyrolactone, sulfolane, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, 1, 2-dibutoxyethane, N-butyl alcohol, N-propyl alcohol, N-butyl alcohol, N, Ethoxy methoxyethane, and the like.

The pretreatment apparatus for an ion exchange resin according to the present invention includes an ion exchange resin container containing an ion exchange resin into which a nonaqueous solvent is introduced.

The ion exchange resin is not particularly limited, but is preferably an organic polymer-based ion exchange resin having an organic polymer as a matrix, and examples of the organic polymer serving as a matrix include a styrene-based resin and an acrylic resin.

In the present specification, a styrene-based resin refers to a resin obtained by homopolymerization or copolymerization of styrene or a styrene derivative and containing 50 mass% or more of structural units derived from styrene or a styrene derivative.

Examples of the styrene derivative include α -methylstyrene, vinyltoluene, chlorostyrene, ethylstyrene, isopropylstyrene, dimethylstyrene, and bromostyrene.

The styrene-based resin may be a copolymer with another copolymerizable vinyl monomer as long as it contains a homopolymer or copolymer of styrene or a styrene derivative as a main component, and examples of the vinyl monomer include at least one selected from the group consisting of divinylbenzene such as o-divinylbenzene, m-divinylbenzene and p-divinylbenzene, polyfunctional monomers such as ethylene glycol di (meth) acrylate and alkylene glycol di (meth) acrylate such as polyethylene glycol di (meth) acrylate, and (meth) acrylonitrile and methyl (meth) acrylate.

The other copolymerizable vinyl monomer is more preferably ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having an ethylene polymerization number of 4 to 16, divinylbenzene, still more preferably divinylbenzene and ethylene glycol di (meth) acrylate, and still more preferably divinylbenzene.

In the present document, the acrylic resin refers to a resin obtained by homopolymerizing or copolymerizing at least one member selected from the group consisting of acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters, and containing 50 mass% or more of a structural unit selected from the group consisting of a structural unit derived from acrylic acid, a structural unit derived from methacrylic acid, a structural unit derived from acrylic acid esters, and a structural unit derived from methacrylic acid esters.

More specifically, the acrylic resin may be selected from homopolymers of acrylic acid, homopolymers of methacrylic acid, homopolymers of acrylic acid esters, homopolymers of methacrylic acid esters, copolymers of acrylic acid with other monomers (for example, acrylic acid esters, methacrylic acid esters, α -olefins (for example, ethylene, divinylbenzene, etc.)), copolymers of methacrylic acid with other monomers (for example, acrylic acid esters, methacrylic acid esters, α -olefins (for example, ethylene, divinylbenzene, etc.), copolymers of acrylic acid esters with other monomers (for example, acrylic acid, methacrylic acid esters, α -olefins (for example, ethylene, divinylbenzene, etc.), copolymers of methacrylic acid esters with other monomers (for example, acrylic acid esters, methacrylic acid esters, divinylbenzene, etc.), copolymers of methacrylic acid esters with other monomers (for example, acrylic acid esters, methacrylic, One or more copolymers of α -olefins (e.g., ethylene, divinylbenzene, etc.)), among which methacrylic acid-divinylbenzene copolymer or acrylic acid-divinylbenzene copolymer is preferable.

The acrylic ester is preferably an alkyl acrylate, more preferably a linear alkyl ester or a branched alkyl ester of acrylic acid, and still more preferably a linear alkyl ester of acrylic acid.

The acrylic ester is more preferably an alkyl acrylate in which the alkyl group contained in the alkyl ester moiety has 1 to 4 carbon atoms, more preferably methyl acrylate or ethyl acrylate, and particularly preferably methyl acrylate.

The methacrylate is preferably an alkyl methacrylate, more preferably a linear alkyl ester or a branched alkyl ester of methacrylic acid, and still more preferably a linear alkyl ester of methacrylic acid.

The methacrylate ester is more preferably an alkyl methacrylate in which the alkyl group contained in the alkyl ester moiety has 1 to 4 carbon atoms, and is further preferably methyl methacrylate or ethyl methacrylate, and particularly preferably methyl methacrylate.

Examples of the ion exchange resin include at least one selected from the group consisting of a cation exchange resin having a cation exchange group, an anion exchange resin having an anion exchange group, and a chelate resin.

Examples of the cation exchange resin include strongly acidic cation exchange resins having a sulfo group as a cation exchange group, and weakly acidic cation exchange resins having a carboxyl group as a cation exchange group.

Examples of the anion exchange resin include strongly basic anion exchange resins having quaternary ammonium groups as anion exchange groups, and weakly basic anion exchange resins having amino groups as anion exchange groups.

In the pretreatment apparatus for an ion exchange resin according to the present invention, a weakly basic ion exchange resin is preferably used as the ion exchange resin into which the nonaqueous solvent stored in the ion exchange resin container is introduced.

The weakly basic ion exchange groups constituting the weakly basic ion exchange resin are preferably primary to tertiary amino groups, and more preferably tertiary amino groups such as dimethylamino groups.

Examples of the weakly basic anion exchange group include a tertiary amino group represented by the following general formula (I).

[ chemical formula 1 ]

(in the formula, R¹Group and R²The groups are hydrocarbon groups having 1 to 3 carbon atoms, and may be the same or different from each other, and represent a bonding site with a substrate or a bonding site with a bonding group for bonding with a substrate. )

In the weakly basic anion exchange group represented by the above general formula (I), R¹Group and R²The group is a hydrocarbon group having 1 to 3 carbon atoms.

As R¹Group or R²Examples of the group include one or more selected from an alkyl group and an alkenyl group, and examples thereof include an alkyl group.

As R¹Group or R²Specific examples of the group include at least one selected from the group consisting of a methyl group, an ethyl group, a propyl group and a propylene group, and a methyl group is preferable.

In the weakly basic anion exchange group represented by the above general formula (I), R¹Group and R²The groups may be the same or different from each other.

Examples of the weakly basic anion exchange group represented by the above general formula (I) include dimethylamino group, diethylamino group, dipropylamino group, etc., and dimethylamino group is preferable.

In the general formula (I), the bonding site between the weakly basic anion exchange group represented by the general formula (I) and the substrate or the bonding site between the weakly basic anion exchange group represented by the general formula (I) and the bonding group for bonding to the substrate is represented.

The weakly basic anion exchange group represented by the above general formula (I) is preferably represented by the following general formula (II) with respect to a matrix containing a styrene-based resin, through an appropriate bonding group, namely R³And bonding the groups.

[ chemical formula 2 ]

(in the formula, R¹Group and R²The groups are hydroxyl groups having 1 to 3 carbon atoms, and may be the same or different, R³The group is a hydrocarbon group having 1 to 3 carbon atoms, and represents a bonding site with the substrate. )

As the above-mentioned R¹Group and R²Examples of the group include the same groups as described above.

R is as defined above³The group is a C1-3 hydrocarbon group as R³Examples of the group include at least one selected from the group consisting of an alkylene group and an alkenylene group, and an alkylene group is preferable.

As R³Specific examples of the group include methylene (-CH)₂-) ethylene (-CH₂CH₂-) propylene (-CH)₂CH₂CH₂-) and the like, preferably a methylene group.

The weakly basic anion exchange group represented by the above general formula (I) can be introduced into the styrene-based resin by introducing it as a substituent into styrene or a styrene derivative.

The anion exchange resin can be a commercial product, for example can be selected from Mitsubishi chemical corporation DIAION WA30, ORGANO corporation ORLITES DS-6 and more.

The ion exchange resin contained in the ion exchange resin container may be an ion exchange resin having a gel-type structure, an ion exchange resin having a macroporous network-type (MR-type) structure, an ion exchange resin having a macroporous (MP-type) structure, or an ion exchange resin having a porous structure.

The size of the ion exchange resin contained in the ion exchange resin container is not particularly limited, and the harmonic mean diameter is preferably 300 to 1000. mu.m, more preferably 400 to 800. mu.m, and still more preferably 500 to 700. mu.m.

Further, the ion exchange resin contained in the ion exchange resin container preferably has a total ion exchange capacity in a wet state of 0.1 to 3.0(eq/L-R), more preferably 0.5 to 2.5(eq/L-R), and still more preferably 1.0 to 2.0 (eq/L-R).

In the pretreatment apparatus for an ion exchange resin according to the present invention, the storage form of the ion exchange resin stored in the ion exchange resin container is not particularly limited as long as the nonaqueous solvent can be brought into contact with the ion exchange resin.

For example, the ion exchange resin container may be a column or a tank filled with an ion exchange resin, which may be passed through a non-aqueous solvent.

The ion exchange resin container may be provided with a pump for introducing the nonaqueous solvent.

In the ion exchange resin pretreatment apparatus according to the present invention, the liquid flow rate (liquid space rate) of the ion exchange resin for introducing the nonaqueous solvent into the ion exchange resin container may be appropriately selected depending on the rate at which the water in the ion exchange resin can be removed or reduced.

In the pretreatment apparatus for an ion exchange resin according to the present invention, the circulating liquid-feeding pipe is preferably configured to: the nonaqueous solvent flowing through the circulating liquid feeding pipe is introduced so as to flow upward with respect to the ion exchange resin contained in the ion exchange resin container.

That is, as illustrated in fig. 2 and 3, the ion exchange resin pretreatment device 1 according to the present invention preferably has the circulation liquid sending pipe L configured to: the nonaqueous solvent S supplied from the raw-solution tank 2 storing the nonaqueous solvent and flowing therethrough flows upward relative to the ion exchange resin contained in the ion exchange resin container 3.

In this manner, the circulation liquid feeding pipe L is configured such that: the nonaqueous solvent flowing through the circulating liquid feeding pipe is introduced so as to flow upward relative to the ion exchange resin contained in the ion exchange resin container, and even when air bubbles or the like are mixed in the ion exchange resin contained in the ion exchange resin container, the air bubbles in the ion exchange resin can be removed by flowing while being defoamed when the nonaqueous solvent flows upward in the ion exchange resin container.

Therefore, even when air bubbles are mixed in the ion exchange resin contained in the ion exchange resin container, the water in the ion exchange resin can be removed and reduced while the contact between the nonaqueous solvent and the ion exchange resin is maintained appropriately.

The pretreatment device for an ion exchange resin according to the present invention includes a water removal device for removing water from a nonaqueous solvent.

Examples of the moisture removing device include a moisture adsorbing device, a membrane separation device, and a gas-liquid separation device, and preferably a moisture adsorbing device.

When the moisture removal device is a moisture adsorption device, the moisture adsorption device preferably contains zeolite as the moisture adsorbent.

The zeolite contained in the moisture adsorbing device is not particularly limited as long as it can adsorb moisture in the organic nonaqueous solvent, and may be one or more kinds selected from crystalline zeolites.

Examples of the crystalline zeolite include at least one crystalline zeolite selected from the group consisting of a-type, Y-type, X-type, chabazite, ferrierite, ZSM-5, clinoptilolite and the like.

The crystalline zeolite preferably has a Si/Al molar ratio of 1 to 5. When the Si/Al molar ratio is within the above range, the structure is stable, and the adsorption and removal of moisture can be appropriately performed while having an appropriate cation content.

The crystalline zeolite may be a zeolite having a cation replaced with a lithium ion, a calcium ion, or the like, or may be a zeolite that has not been replaced.

The pore diameter of the crystalline zeolite is preferably set to be smallMore preferablyFurther preferred is

When the pore diameter of the crystalline zeolite is in the above range, moisture in the organic nonaqueous solvent can be appropriately adsorbed and removed.

In the present document, the pore diameter refers to a theoretical value estimated from the crystal structure and the retained cation species.

The crystalline zeolite is preferably a spherical or cylindrical zeolite, and is preferably a zeolite having a diameter of 0.5 to 5 mm.

When the crystalline zeolite has a diameter within the above range, the nonaqueous solvent can be suitably impregnated without deteriorating the workability.

In the pretreatment device for an ion exchange resin according to the present invention, the zeolite contained in the moisture adsorption device is not particularly limited as long as it is in a form in which the non-aqueous solvent can contact the zeolite.

For example, the moisture adsorption means may be a column or tank packed with zeolite, which may be passed through a non-aqueous solvent.

The moisture adsorption device may be provided with a pump for introducing the nonaqueous solvent.

In the pretreatment apparatus for an ion exchange resin according to the present invention, the liquid passing rate (liquid space rate) at which the nonaqueous solvent is passed through the zeolite can be appropriately selected depending on the rate at which water in the ion exchange resin can be removed.

In the pretreatment apparatus for an ion exchange resin according to the present invention, the circulating liquid-feeding pipe is preferably configured to: the nonaqueous solvent flowing through the circulating liquid-feeding pipe flows upward relative to the zeolite contained in the moisture adsorption device.

That is, as illustrated in fig. 2 and 3, the ion exchange resin pretreatment device 1 according to the present invention preferably has the circulation liquid sending pipe L configured to: the nonaqueous solvent flowing through the circulation liquid-sending pipe L flows upward through the zeolite contained in the moisture removal device 4.

In this manner, the circulation liquid feeding pipe L is configured such that: the nonaqueous solvent flowing through the circulating liquid feeding pipe is introduced so as to flow upward relative to the zeolite contained in the moisture adsorbing device, and even when bubbles or the like are mixed in the zeolite contained in the moisture adsorbing device, the bubbles in the zeolite can be removed by flowing while defoaming the bubbles when the nonaqueous solvent flows upward in the moisture adsorbing device.

Therefore, even when air bubbles or the like are mixed in the zeolite contained in the moisture adsorption device, the treatment can be performed while appropriately maintaining the contact between the nonaqueous solvent and the zeolite.

As illustrated in fig. 2 and 3, in the pretreatment device for ion exchange resin according to the present invention, the circulation liquid sending pipe L is configured such that: after the non-aqueous solvent S is introduced from the raw-solution tank 2 in the order of the ion exchange resin container 3 and the moisture removal device 4, the introduced non-aqueous solvent S is returned to the raw-solution tank 2 so that the non-aqueous solvent S can continue to circulate (fig. 2), or the configuration is such that: after the non-aqueous solvent is introduced from the raw-solution tank 2 in the order of the moisture removal device 4 and the ion exchange resin container 3, the introduced non-aqueous solvent is returned to the raw-solution tank, and the non-aqueous solvent S can be continuously circulated (fig. 3).

In the pretreatment device for an ion exchange resin according to the present invention, the circulation liquid supply pipe is configured to: the non-aqueous solvent in the stock solution tank is circulated through the ion exchange resin vessel and the water removal device, and the ion exchange resin is pretreated while repeatedly eluting the water remaining in the ion exchange resin into the non-aqueous solvent and adsorbing and removing the water eluted from the non-aqueous solvent by the water removal device. Therefore, in the pretreatment apparatus for an ion exchange resin according to the present invention, the water content in the ion exchange resin can be reduced simply and economically by allowing only a small amount of the nonaqueous solvent to flow through the flow path of the circulation liquid-sending pipe.

The pretreatment device for ion exchange resin according to the present invention may further include a filtration device at a stage (downstream side) subsequent to the moisture removal device.

In the pretreatment device for an ion exchange resin according to the present invention, the amount of the nonaqueous solvent used for the pretreatment of the ion exchange resin is preferably 1 to 30 times, more preferably 1 to 20 times, and still more preferably 1 to 10 times the volume of the ion exchange resin per unit volume of the ion exchange resin in the ion exchange resin container.

In the ion exchange resin pretreatment device according to the present invention, the circulation amount of the nonaqueous solvent flowing through the circulation/supply pipe may be appropriately selected in accordance with the circulation amount of the ion exchange resin in which the adsorbed water is reduced to a desired level.

In the pretreatment apparatus for an ion exchange resin according to the present invention, after the water removal treatment of the ion exchange resin is performed to a desired degree, the same nonaqueous solvent as that used in the removal treatment may be used as it is.

When a solvent different from the nonaqueous solvent used for removing water in the ion exchange resin is treated, for example, the nonaqueous solvent to be treated is introduced and the nonaqueous solvent used for the pretreatment is replaced, and then the treatment is performed.

In addition, after the reverse washing and extrusion operation are carried out according to the conventional method, the preferable SV (flow rate/volume ratio of ion exchange resin) is used for 1-100 hr^-1More preferably SV 2-50 hr^-1More preferably SV 5-20 hr^-1The method (2) is to introduce a nonaqueous solvent to be treated.

According to the present invention, it is possible to provide an apparatus for pretreating an ion exchange resin, which can reduce the water content simply and economically.

Next, a method for pretreating an ion exchange resin according to the present invention will be described.

The method for pretreating an ion exchange resin according to the present invention is a method for pretreating an ion exchange resin, comprising feeding a liquid while circulating a nonaqueous solvent, the method comprising: a raw liquid tank storing a nonaqueous solvent; an ion exchange resin container that contains an ion exchange resin; and a water removing device for removing water in the nonaqueous solvent; the liquid delivery is selected from one or more of the following: a liquid feed from the raw liquid tank to the raw liquid tank after introducing a nonaqueous solvent in the order of the ion exchange resin container and the moisture removal device, and a liquid feed from the raw liquid tank to the raw liquid tank after introducing a nonaqueous solvent in the order of the moisture removal device and the ion exchange resin container.

The method for pretreating an ion exchange resin according to the present invention substantially relates to a method for pretreating an ion exchange resin using the apparatus for pretreating an ion exchange resin according to the present invention, and the details of the method for pretreating an ion exchange resin are common to the description of the above-mentioned mode of use of the apparatus for pretreating an ion exchange resin according to the present invention.

According to the present invention, a pretreatment method of an ion exchange resin can be provided, which can reduce the water content simply and economically.

[ examples ] A method for producing a compound

The present invention will be described more specifically with reference to examples, but the examples are merely illustrative and do not limit the present invention.

In the following examples and comparative examples, the amount of water (mass ppm) in the organic nonaqueous solvent before the treatment and the amount of water (mass ppm) in the organic nonaqueous solvent after the treatment are values measured by the karl fischer method.

The amount of Al (mass ppb) in the organic nonaqueous solvent is a value measured by inductively coupled plasma mass spectrometry (ICP-MS), and corresponds to the amount of zeolite flowing out of the moisture removal device.

(example 1)

The pretreatment of the ion exchange resin in the ion exchange resin container 3 was performed using the pretreatment device 1 for ion exchange resin shown in fig. 2.

That is, as shown in fig. 2, the liquid stored in the raw liquid tank 2 is transferred to the liquid tank 2 by a pump P in a volume ratio of 1: 1 (moisture content less than 10 mass ppm) of an organic nonaqueous solvent S obtained by mixing ethylene carbonate and dimethyl carbonate is introduced from the bottom of an ion exchange resin container 3 containing a weakly basic anion exchange resin (MR type anion exchange resin having a styrene resin as a matrix and having dimethylamino groups as weakly basic anion exchange groups) so as to flow upward in the direction of the top at a flow rate of 10 (L/L-resin)/h, and crystalline A-type zeolite (having a pore diameter of less than 10 mass ppm) is contained in the container) The water removal device 4 of (4) above, wherein the organic nonaqueous solvent flowing out is introduced from the bottom to the top thereof so as to flow upward at a flow velocity of 5 (L/L-zeolite)/h, and the organic nonaqueous solvent flowing out is returned to the raw liquid tank 2. After the treatment was continued for 10 hours and the organic nonaqueous solvent was circulated in the pretreatment device 1, the amount of water in the organic nonaqueous solvent flowing out from the ion exchange resin container 3 was measured, and as a result, the amount was less than 10 mass ppm. Further, the amount of Al in the organic nonaqueous solvent extracted from the raw-solution tank 2 was measured, and as a result, 16 mass ppb was obtained.

The volume of the organic nonaqueous solvent S used per unit volume of the ion exchange resin was 10 times.

(example 2)

The ion exchange resin pretreatment was performed in the same manner as in example 1 except that water was added to the organic nonaqueous solvent before the treatment in the ion exchange resin pretreatment apparatus 1 in example 1 and the organic nonaqueous solvent S having a water content of 20 mass ppm was used. The amount of water in the organic nonaqueous solvent flowing out of the ion exchange resin container 3 was measured, and as a result, it was less than 10 mass ppm.

The volume of the organic nonaqueous solvent S used per unit volume of the ion exchange resin was 10 times.

(example 3)

The pretreatment of the ion exchange resin in the ion exchange resin container 3 was performed using the pretreatment device 1 for ion exchange resin shown in fig. 4.

That is, as shown in fig. 4, the liquid stored in the raw liquid tank 2 is transferred to the liquid tank by a pump P in a volume ratio of 1: 1 (at a water content of 10 ppm by mass), from the bottom of an ion exchange resin container 3 containing a weakly basic anion exchange resin (MR type anion exchange resin having a styrene resin as a matrix and having dimethylamino groups as weakly basic anion exchange groups), the organic nonaqueous solvent S (at a water content of 10 ppm by mass) is introduced so as to flow upward in the direction of the ceiling at a flow rate of 10 (L/L-resin)/h, and contains crystalline A-type zeolite (having a pore diameter of 10 ppm)) The water removal device 4 in (2) was a device in which the organic nonaqueous solvent flowed out was introduced from the bottom to the top so as to flow upward at a flow rate of 5 (L/L-zeolite)/h, and then the organic nonaqueous solvent flowed out was placed in a filtration device F containing a polypropylene filter medium having a pore size of 1 μm at a flow rate of 0.53ml/(h cm)²) The filtration rate of (2) is fed in an upward flow manner, and the organic nonaqueous solvent flowing out is returned to the raw liquid tank 2. After the treatment was continued for 10 hours and the organic nonaqueous solvent was circulated in the pretreatment device 1, the amount of water in the organic nonaqueous solvent flowing out from the ion exchange resin container 3 was measured, and as a result, the amount was less than 10 mass ppm. Further, the amount of Al in the organic nonaqueous solvent collected from the raw-solution tank 2 was measured, and as a result, it was 3 ppb by mass.

The volume of the organic nonaqueous solvent S used per unit volume of the ion exchange resin was 10 times.

Comparative example 1

The pretreatment of the ion exchange resin in the ion exchange resin container 3 was performed using the pretreatment device 11 for ion exchange resin shown in fig. 5.

That is, as shown in fig. 5, the liquid stored in the raw liquid tank 2 is transferred by a pump P in a volume ratio of 1: an organic nonaqueous solvent S (moisture content: less than 10 mass ppm) obtained by mixing ethylene carbonate and dimethyl carbonate at a ratio of 1 is introduced from the bottom of an ion exchange resin container 3 containing a weakly basic anion exchange resin (MR type anion exchange resin having a styrene resin as a matrix and having dimethylamino groups as weakly basic anion exchange groups) so as to flow upward in the direction of the top at a flow rate of 10 (L/L-resin)/h, and the organic nonaqueous solvent W thus discharged is stored in a storage tank 5.

The amount of water in the organic nonaqueous solvent flowing out of the ion exchange resin container 3 was measured, and the result was 150 mass ppm.

The volume of the organic nonaqueous solvent S used per unit volume of the ion exchange resin was 10 times.

Comparative example 2

The pretreatment of the ion exchange resin was carried out in the same manner as in comparative example 1 except that the organic nonaqueous solvent S was used in an amount of 100 times the volume of the ion exchange resin per unit volume in comparative example 1. The amount of water in the organic nonaqueous solvent flowing out of the ion exchange resin container 3 was measured, and as a result, it was less than 10 mass ppm.

Comparative example 3

The ion exchange resin pretreatment was performed in the same manner as in comparative example 2, except that in comparative example 2, water was added to the organic nonaqueous solvent before the treatment in the ion exchange resin pretreatment apparatus 11, and the organic nonaqueous solvent S having a water content of 20 mass ppm was used. The amount of water in the organic nonaqueous solvent flowing out of the ion exchange resin container 3 was measured, and the result was 20 mass ppm.

The volume of the organic nonaqueous solvent S used per unit volume of the ion exchange resin is 100 times.

The results of the above examples and comparative examples are shown in table 1.

[ TABLE 1 ]

*: "< 10" means less than 10 mass ppm.

As is apparent from table 1, in the ion exchange resin pretreatment apparatus 1 in examples 1 to 3, since the organic nonaqueous solvent S is introduced from the raw liquid tank 2 in the order of the ion exchange resin container 3 and the water removal device 4, and then the introduced nonaqueous solvent is returned to the raw liquid tank 2 to be circulated, the water content of the ion exchange resin contained in the ion exchange resin container 3 can be highly reduced easily and economically.

Further, in example 3, since the filtration device F is further provided downstream of the moisture removal device, the amount of Al in the organic nonaqueous solvent can be reduced and the contamination of zeolite particles into the ion exchange resin container can be suppressed as compared with the pretreatment device 1 of example 1 not having the above-described filtration device F.

On the other hand, as is clear from table 1, in comparative example 1, the pretreatment device 11 for ion exchange resin does not have the circulation liquid feeding tube L for feeding the treatment liquid back to the moisture removal device 4 and the raw liquid tank 2, and the organic nonaqueous solvent is not circulated, and the moisture content of the ion exchange resin cannot be sufficiently reduced even when the same amount of the nonaqueous solvent is used.

As is clear from table 1, in comparative example 2, since the pretreatment device 11 for ion exchange resin does not have the circulation liquid sending tube L for returning the treatment liquid to the moisture removal device 4 and the raw liquid tank 2 and does not use the organic nonaqueous solvent in a circulating manner, the amount of the organic nonaqueous solvent required in the pretreatment device for ion exchange resin is 10 times that of example 1 in order to reduce the moisture amount of the organic nonaqueous solvent flowing out of the ion exchange resin to the same level as that of example 1.

Further, as is clear from table 1, in comparative example 3, since the pretreatment device 11 for ion exchange resin does not have the circulation liquid sending tube L for returning the treatment liquid to the moisture removal device 4 and the raw liquid tank 2, and the organic nonaqueous solvent is not used in a circulating manner, when the amount of water in the organic nonaqueous solvent before treatment is as large as 20 mass ppm, the water content of the ion exchange resin cannot be sufficiently reduced even by using the organic nonaqueous solvent in an amount of 10 times as much as that of example 1.

Industrial applicability

According to the present invention, it is possible to provide an apparatus and a method for pretreating an ion exchange resin, which can reduce the water content simply and economically.

Description of the symbols

1: ion exchange resin's preprocessing device

2: stock solution pot

3: ion exchange resin container

4: moisture removing device

5: a storage tank.