JP6024416B2 - Ultrapure water production method and ultrapure water production apparatus - Google Patents

Description

  The present invention relates to a method and an apparatus for producing ultrapure water using an ultrapure water production apparatus provided with an anion exchange resin.

  Ultrapure water is used in various applications such as cleaning water used in manufacturing processes for semiconductors, liquid crystals, wafers, precision parts, etc., demineralized water produced in power plant condensate demineralizers, and pharmaceutical production water. Yes. Usually, these ultrapure waters are MF (microfiltration) membrane, UF (ultrafiltration) membrane, RO (reverse osmosis filtration) membrane, ion exchange resin, EDI (continuous electric regenerative pure water system), UV water sterilization A wide variety of devices such as devices and degassing devices are used and manufactured in combination.

  Among these, the ion exchange resin is used as a main member. Such ultrapure water production processes include a system in which the ion exchange resin tower is mainly used in a single bed, a system in which the ion exchange resin tower is used in a mixed bed, and a system in which these are combined. Among these, representatively exemplified processes for producing ultrapure water are roughly classified into pretreatment, primary system, secondary system (also referred to as subsystem), and drainage system. Among these, the primary system is a system for producing primary pure water having a purity increased from raw water, and the secondary system is a system for further purifying the primary pure water produced by the primary system, These primary and secondary systems are often provided with ion exchange resin towers (Non-patent Document 1).

  Of the ion exchange resins used in the ion exchange resin tower of the ultrapure water production system, the primary system usually regenerates and reuses the ion exchange resin, so low elution (from the ion exchange resin during water flow) Resin with high cycle strength (durability against repeated regeneration and reuse) is required. Also, in the ion exchange resin used in the secondary system, it is desirable that the resin can be regenerated and reused, and the same function as that of the primary system is required.

  By the way, ion exchange resins are roughly classified into “gel type” and “porous (porous) type”, and there are cation exchange resins and anion exchange resins, respectively. The gel type resin has an ion exchange capacity per volume larger than that of the porous type, and is considered advantageous for the production of ultrapure water. However, the gel type resin has a drawback that the cycle strength is lower than that of the porous type. Gel type resins generally have a smaller specific surface area than porous type resins, so there is no problem adsorbing ordinary inorganic ions (such as chloride ions), but to adsorb high molecular weight substances. It is disadvantageous.

  Moreover, since an ion exchange resin is generally an organic substance in which a functional group is introduced into a styrene-divinylbenzene crosslinked copolymer, an organic component derived from the ion exchange resin is eluted when used for water treatment. For example, polystyrene sulfonic acid having a molecular weight of several hundred to several tens of thousands is eluted from the cation exchange resin due to oxidative degradation of the base structure. Gel type anion exchange resin is contained in raw water (water before being treated with ion exchange resin) because it is inferior in adsorption performance of such high molecular weight materials compared to porous type anion exchange resin. The ion exchange capacity may be impaired by the organic matter that is produced and polystyrene sulfonic acid eluted from the cation exchange resin. Furthermore, there is also a problem that the anion exchange resin is contaminated with organic matter by the organic matter derived from the raw water or the effluent of the cation exchange resin. Anion exchange resins that have been contaminated with organic matter have a reduced reaction rate, and as a result, leakage of organic matter (a TOC value as a measurement value) to the ultrapure water after treatment must be performed. Arise. For this reason, an anion exchange resin is desired that has a high ability to adsorb organic components and can be used for a long period of time.

  In addition, about the method of reducing the anion exchange resin-derived organic substance component and making it into a low elution anion exchange resin, the method (patent document 1) which wash | cleans an anion exchange resin with an organic solvent, anion exchange resin A method of washing with a water-soluble organic solvent after heat treatment in an alkaline aqueous solution (Patent Document 2) is known. Recently, a method of aging treatment of an anion exchange resin in a sealed state (Patent Document 3) has also been proposed.

Japanese Patent Laid-Open No. 5-15789 JP 2004-41915 A JP 2007-83132 A

"Pure water and ultra pure water technology understood by this" Supervision of Kurita Kogyo Co., Ltd. First edition issued on November 18, 2004

  The present invention is easier than the conventional method for producing ultrapure water using an anion exchange resin, and high purity ultrapure water has a high cycle strength, and the organic substance elution amount is stable and efficient over a long period of time. It is an object of the present invention to provide an ultrapure water production method and an ultrapure water production apparatus capable of producing reduced ultrapure water.

  As a result of intensive studies to solve the above problems, the present inventor solved the above problems by using a specific gel-type strongly basic anion exchange resin as the anion exchange resin of the ultrapure water production apparatus. Found that you can.

That is, the gist of the present invention is the following [1] to [ 8 ].

[1] In a method for producing ultrapure water using an ultrapure water production apparatus equipped with an anion exchange resin, the anion exchange resin is a gel type, and the polystyrene sulfonic acid adsorption amount measured by the following method Is a 0.25 mmol / L-resin or more and a strong basic anion exchange resin having an average particle diameter of 300 μm or more and 1000 μm or less is used.
<Measurement method of polystyrene sulfonic acid adsorption amount>
Polystyrene sulfonic acid “Polynas PS-1” manufactured by Tosoh Organic Chemical Co., Ltd. was passed through a strongly acidic cation exchange resin to form H, and then the polystyrene sulfonic acid adjusted to an H concentration of 0.01 mmol / L. Prepare an aqueous solution.
The column is filled with a strongly basic anion exchange resin that has been adjusted to OH form by treatment with an aqueous sodium hydroxide solution, washed with water, and then passed through a polystyrenesulfonic acid aqueous solution with a concentration adjusted to give polystyrene equivalent to 50% breakthrough. The amount of sulfonic acid adsorbed is determined and taken as the amount of polystyrene sulfonic acid adsorbed by the strongly basic anion exchange resin.

[2] The ultrapure according to [1], wherein the anion exchange resin is a strongly basic anion exchange resin having a specific surface area of less than 1 m ² / g measured by a BET adsorption method using krypton as an adsorption gas. Water production method.

[3] The [1] or [2], wherein the anion exchange resin is a strongly basic anion exchange resin having an absorbance determined from a reflectance of light having a wavelength of 800 nm of 0.10 to 0.44. Manufacturing method of ultrapure water.

[4] The anion exchange resin is heat-treated in the presence of an alkaline aqueous solution and washed with a liquid containing 50% by weight or more of a water-soluble organic solvent. [1] Thru | or the manufacturing method of the ultrapure water in any one of [3].

[5 ] Any of [1] to [ 4 ], wherein the ultrapure water production apparatus is a multi-bed ultrapure water production apparatus having a strongly acidic cation exchange resin layer and a layer of the anion exchange resin. The manufacturing method of the ultrapure water of crab.

[6] The ultrapure water production system is an ultrapure water production system of mixed bed having a layer comprising a mixture of strongly acidic cation exchange resin and the anion exchange resin, [1] to [4 ] The manufacturing method of the ultrapure water in any one of.
[ 7 ] The method for producing ultrapure water according to any one of [1] to [ 6 ], wherein the ultrapure water device is applied to a secondary system of a process for producing ultrapure water.

[ 8 ] An ultrapure water production apparatus provided with an anion exchange resin, which is a gel type as the anion exchange resin, and has an adsorption amount of polystyrene sulfonic acid measured by the following method of 0.25 mmol / L- An ultrapure water production apparatus comprising a strongly basic anion exchange resin that is not less than a resin and has an average particle size of not less than 300 μm and not more than 1000 μm.
<Measurement method of polystyrene sulfonic acid adsorption amount>
Polystyrene sulfonic acid “Polynas PS-1” manufactured by Tosoh Organic Chemical Co., Ltd. was passed through a strongly acidic cation exchange resin to form H, and then the polystyrene sulfonic acid adjusted to an H concentration of 0.01 mmol / L. Prepare an aqueous solution.
The column is filled with a strongly basic anion exchange resin that has been adjusted to OH form by treatment with an aqueous sodium hydroxide solution, washed with water, and then passed through a polystyrenesulfonic acid aqueous solution with a concentration adjusted to give polystyrene equivalent to 50% breakthrough. The amount of sulfonic acid adsorbed is determined and taken as the amount of polystyrene sulfonic acid adsorbed by the strongly basic anion exchange resin.

  The strongly basic anion exchange resin used in the present invention has the advantage of a gel type resin having a large ion exchange capacity per volume as compared with the porous type, and has a high cycle strength, and from a cation exchange resin such as polystyrene sulfonic acid. Since the porous resin has the advantage that the adsorbed amount of organic components such as the eluate of the raw material and the organic matter derived from raw water is high, it can be used for a long time and has low elution. Therefore, using this strongly basic anion exchange resin, it is preferable that ultrapure water with high purity be provided over a long period of time using an ultrapure water production apparatus preferably comprising this strongly basic anion exchange resin and a strongly acidic cation exchange resin. It can be manufactured stably and efficiently.

  Embodiments of the present invention will be described in detail below, but the present invention is not limited to the following descriptions, and can be arbitrarily modified and implemented without departing from the gist of the present invention. In addition, in this specification, when expressing by putting a numerical value or a physical-property value before and behind using "-", it shall use as what includes the value before and behind.

  The ultrapure water production method of the present invention is a gel-type strong base having specific physical properties as anion exchange resin when producing ultrapure water using an ultrapure water production apparatus equipped with an anion exchange resin. A characteristic anion exchange resin is used.

In the present invention, “ultra-pure water” is defined as water passed through the gel-type strongly basic anion exchange resin used in the present invention, and is an organic substance measured by the method described in the examples below. The amount of elution is preferably 50 ppb or less, more preferably 35 ppb or less, and particularly preferably 20 ppb or less.
In the following, the specific strong base anion exchange resin used in the present invention may be referred to as “strong base anion exchange resin of the present invention”. Moreover, the ultrapure water production apparatus provided with the strongly basic anion exchange resin of the present invention used for the production of the ultrapure water of the present invention may be referred to as “the ultrapure water production apparatus of the present invention”.

  In the ultrapure water production apparatus of the present invention, the strongly basic anion exchange resin of the present invention is preferably used together with a strongly acidic cation exchange resin described later. In this case, the strongly basic anion exchange resin of the present invention effectively exhibits the effect of being excellent in the adsorption performance of the effluent from the strongly acidic cation exchange resin.

[Strongly basic anion exchange resin]
The strongly basic anion exchange resin of the present invention is a gel-type resin, and the polystyrenesulfonic acid adsorption amount measured by a specific method is 0.25 mmol / L-resin or more, and the average particle size is 300 μm. It is the above. In the present invention, “strongly basic anion exchange resin” means a basic anion exchange resin having a quaternary ammonium group as an exchange group. Preferable examples of the exchange group of the strongly basic anion exchange resin include a trimethylammonium group and a dimethylethanolammonium group. Among these exchange groups, those having a trimethylammonium group are preferred from the viewpoints of basic strength and chemical stability.

<Gel type>
The strongly basic anion exchange resin of the present invention is characterized by being a gel type.

  As described above, the ion exchange resins are roughly classified into two types, “gel type” and “porous type”, according to their structures. Since the strongly basic anion exchange resin of the present invention is a gel type, the ion exchange capacity per volume is larger than that of a porous resin.

  As a method for discriminating between the gel type and the porous type, there is a method in which the transparent sphere is visually discriminated as a gel type resin and the opaque sphere is discriminated as a porous type resin as described in JP-A-2009-279519.

  As described above, the gel type resin has an advantage that the ion exchange capacity per volume is larger than that of the porous type. On the other hand, gel type resins generally have a smaller specific surface area than porous type resins, so there is no problem in adsorbing inorganic ions (such as chloride ions), but it is disadvantageous for adsorbing high molecular weight substances. It is. That is, as described above, polystyrene sulfonic acid having a molecular weight of several hundred to several tens of thousands elutes from the cation exchange resin due to oxidative degradation of the base structure, etc., but the ability to adsorb and remove this is a gel type resin. Low compared to Further, the gel type resin has a lower cycle strength than the porous type resin.

  As a result of intensive studies, the present inventor has developed a resin that combines the advantages of a gel type resin with a large ion exchange capacity, and the advantage of a porous type resin with high polystyrene sulfonic acid adsorption ability and high cycle strength. The present invention has been reached. That is, a general gel type resin synthesizes a cross-linked copolymer by copolymerizing a monovinyl aromatic monomer such as styrene and a cross-linkable aromatic monomer such as divinylbenzene by suspension polymerization or the like. Introduced and manufactured. On the other hand, although the method for synthesizing the porous resin differs depending on each manufacturer, in general, an inert substance (hereinafter sometimes referred to as “porous agent”) is added during suspension polymerization, and after the polymerization, A method of removing this is adopted. Examples of the porosifying agent include organic solvents such as toluene, pentanol, s-butanol, heptane, and isooctane, or dilutions of linear polymers, specifically, toluene in which polystyrene is dissolved. At this time, the abundance of the porous portion is determined by the degree of crosslinking (addition amount of the crosslinkable aromatic monomer) and the balance between the kind of the porous agent and the addition amount.

  In the present invention, it is added when synthesizing a general porous resin when synthesizing a cross-linked copolymer by polymerizing a monovinyl aromatic monomer such as styrene and a cross-linkable aromatic monomer such as divinylbenzene. By using the above-mentioned porosifying agent and adjusting the addition amount, it is a gel type resin and has the advantage of high polystyrene sulfonic acid adsorption ability of porous type resin and high cycle strength. A strongly basic anion exchange resin was obtained.

  Furthermore, the strongly basic anion exchange resin of the present invention can be further improved in low elution by performing the specific treatment described below. The specific treatment means that the strongly basic anion exchange resin of the present invention is subjected to a heat treatment in the presence of an alkaline aqueous solution and subjected to a washing treatment with a liquid containing 50% by weight or more of a water-soluble organic solvent. It is. The strongly basic anion exchange resin of the present invention has a structure that widens the network of the cross-linked structure with respect to the conventional gel type anion exchange resin, so the residual organic matter in the resin is well washed, and this treatment is performed. As a result, the strongly basic anion exchange resin of the present invention achieves better and lower elution, and high purity ultrapure water is stable and efficient over a long period of time as an anion exchange resin for ultrapure water production equipment. Can be manufactured.

<Average particle size>
The strongly basic anion exchange resin of the present invention is characterized by having an average particle size of 300 μm or more.

If the average particle size of the strongly basic anion exchange resin is smaller than 300 μm, the pressure loss during water flow in the resin packed bed will increase, and a large-capacity pump will be required for liquid feeding, or a pressure vessel should be used. It becomes disadvantageous for practical use. However, if the average particle size of the strongly basic anion exchange resin is too large, the surface area per volume becomes small and the reaction rate of ion exchange tends to decrease, or the strength of the resin tends to be difficult to maintain. Therefore, the average particle size of the strongly basic anion exchange resin is 300 μm or more, preferably 400 μm or more, on the other hand, preferably 1000 μm or less, more preferably 800 μm or less. In addition, the average particle diameter of the strongly basic anion exchange resin is a value measured by the method described in the section of Examples described later.

<Polystyrenesulfonic acid adsorption amount>
The strongly basic anion exchange resin of the present invention is characterized in that the polystyrenesulfonic acid adsorption amount measured by a specific method is 0.25 mmol / L-resin or more.

  If the strongly basic anion exchange resin has an adsorption amount of polystyrene sulfonic acid of less than 0.25 mmol / L-resin, the adsorption performance of the effluent from the cation exchange resin and organic components is insufficient. Since the polystyrene sulfonic acid adsorption amount is 0.25 mmol / L-resin or more, the eluate such as polystyrene sulfonic acid from the cation exchange resin and the organic matter derived from the raw water are efficiently adsorbed over a long period of time. Leakage of organic components into ultrapure water can be prevented, and the quality of the obtained ultrapure water can be improved. In addition, the cycle strength is high, and it can sufficiently withstand repeated reproduction and reuse.

  The polystyrene sulfonic acid adsorption amount of the strongly basic anion exchange resin is preferably as high as possible, and more preferably 0.27 mmol / L-resin or more, and particularly preferably 0.29 mmol / L-resin or more. Furthermore, this polystyrene sulfonic acid adsorption amount is usually 0.5 mmol / L-resin or less.

  In addition, the polystyrene sulfonic acid adsorption amount of the strongly basic anion exchange resin is more specifically measured by the method described in the section of Examples described later.

  The strong basic anion exchange resin of the present invention has a high polystyrene sulfonic acid adsorption capability because it has a structure that expands the network of the cross-linked structure with respect to the conventional gel type anion exchange resin. The constitution that the polystyrene sulfonic acid adsorption amount measured by the method is 0.25 mmol / L-resin or more means that the strongly basic anion exchange resin of the present invention has such a structure. In addition, the strong basic anion exchange resin of the present invention, which has a high adsorption ability of polystyrene sulfonic acid, has a higher cycle strength than the conventional gel type anion exchange resin. This is because the energy of the volume change of the resin at the time of salt form conversion can be relaxed by adopting a structure in which the network of the crosslinked structure is widened.

  Further, as described above, the strongly basic anion exchange resin of the present invention having a high adsorption ability of polystyrene sulfonic acid has a high adsorption ability of organic components, and is a gel type resin, but it is longer than a normal gel type resin. It has the feature that it can be used.

<Specific surface area>
The strongly basic anion exchange resin of the present invention preferably has a specific surface area of less than 1 m ² / g measured by a BET adsorption method using krypton as an adsorption gas.

That is, since the strongly basic anion exchange resin of the present invention is not a porous resin such as a porous resin but a gel resin, its specific surface area is small, preferably less than 1 m ² / g. When the specific surface area of the strongly basic anion exchange resin is 1 m ² / g or more, it approximates to a porous resin and is inferior in ion exchange capacity per volume. Although there is no restriction | limiting in particular about the minimum of the specific surface area of a strongly basic anion exchange resin, it is a measurement limit (usually 0.01 m < ² > / g).

  The specific surface area of the strongly basic anion exchange resin is a value measured by the method described in the Examples section described later.

<Absorbance>
The strongly basic anion exchange resin of the present invention preferably has an absorbance (hereinafter sometimes referred to as “specific absorbance”) determined from the reflectance of light having a wavelength of 800 nm of 0.10 to 0.44.

  A strongly basic anion exchange resin having a specific absorbance that is too low has low transparency, which means that it is a porous type rather than a gel type, resulting in a low ion exchange capacity per volume. . On the other hand, the one having a large specific absorbance has the transparency of the gel-type resin, but if the specific absorbance is too large, the polystyrene sulfonic acid adsorption amount decreases and the cycle strength also decreases. When the specific absorbance of the strongly basic anion exchange resin is in the above range, the polystyrene sulfonic acid adsorption amount and cycle strength and the ion exchange capacity per volume are sufficient, which is preferable. The specific absorbance of the strongly basic anion exchange resin is more preferably 0.20 to 0.42, and particularly preferably 0.30 to 0.40.

  The specific absorbance of the strongly basic anion exchange resin is more specifically measured by the method described in the Examples section described later.

In the examples described later, the sample having a particle size adjusted to about 600 μm is used as a sample for specific absorbance measurement. However, in the case of a sample having a particle size other than 600 μm (however, it must be a uniform particle size) The value of the converted absorbance obtained from the particle size Rμm and the actually measured absorbance by the following formula may be used as the specific absorbance.
For example, an anion exchange resin having an average particle size (R) of 450 μm or less and a highly uniform particle size distribution, such as an anion exchange resin that is difficult to adjust the particle size to about 600 μm, use the following calculation formula: From the measured absorbance, the specific absorbance of the sized product of about 600 μm can be corrected.
(Conversion Absorbance) = (Measured Absorbance) x (600 / R)

<Cycle strength>
The strongly basic anion exchange resin of the present invention has an appearance index (perfect sphere ratio) described later as 55% or more as an index of cycle strength measured by the method described in the Examples section below. Is preferable for satisfying the practical cycle strength. The appearance index (perfect sphere ratio) is preferably as large as possible, more preferably 65% or more, and still more preferably 80% or more.

<Other physical properties>
The strongly basic anion exchange resin of the present invention has a good demineralization performance of the ion exchange resin that the amount of water measured by the method described in the Examples section below is in the following range. This is preferable. If the amount of water is too small, the substance diffusion in the ion exchange resin is suppressed, and the desalting property may be inhibited. Therefore, the amount is preferably 40% or more, more preferably 45% or more. On the other hand, if the amount is too large, the exchange capacity per volume of the ion exchange resin is lowered and the desalting ability may be lowered, so that it is preferably 60% or less, more preferably 55% or less.

  The strongly basic anion exchange resin of the present invention preferably has an anion exchange performance with a neutral salt decomposition ability of 1.1 meq / mL or more as measured by the method described in the Examples section below. The neutral salt decomposition ability is preferably as large as possible, more preferably 1.2 meq / mL or more.

<Manufacturing method>
The method for producing a strongly basic anion exchange resin of the present invention is a method capable of producing a gel-type strongly basic anion exchange resin satisfying the polystyrene sulfonic acid adsorption amount and the average particle size defined in the present invention. There is no particular limitation, but a specific example is as follows.

  The production process of the strongly basic anion exchange resin of the present invention is roughly divided into (a) a polymerization process, (b) a haloalkylation process, and (c) an amination process.

  (A) In the polymerization step, when a cross-linked copolymer is produced by copolymerizing a mixture of a monovinyl aromatic monomer and a cross-linkable aromatic monomer (hereinafter sometimes referred to as “monomer mixture”), Copolymerization is performed by adding an agent.

  Examples of the monovinyl aromatic monomer include alkyl-substituted styrenes such as styrene, methylstyrene, and ethylstyrene, and halogen-substituted styrenes such as bromostyrene. These may be used alone or in combination of two or more. Among the monovinyl aromatic monomers, styrene or a monomer mainly composed of styrene is preferable.

  In addition, as the crosslinkable aromatic monomer, divinylbenzene, trivinylbenzene, divinyltoluene, divinylnaphthalene, divinylxylene, divinylbiphenyl, bis (vinylphenyl) methane, bis (vinylphenyl) ethane, bis (vinylphenyl) propane, And bis (vinylphenyl) butane. These may be used alone or in combination of two or more. Of these, divinylbenzene is preferred as the crosslinkable aromatic monomer. In addition, although industrially produced divinylbenzene usually contains a large amount of ethyl vinylbenzene (ethylstyrene) as a by-product, such divinylbenzene can also be used in the present invention.

The use amount of the crosslinkable aromatic monomer is usually 0.5 to 30% by weight, preferably 2.5 to 12% by weight, more preferably based on the weight of the mixture of the monovinyl aromatic monomer and the crosslinkable aromatic monomer. 4 to 10% by weight. In the present invention, the use amount of the crosslinkable monomer relative to the weight of the mixture of the monovinyl aromatic monomer and the crosslinkable aromatic monomer is defined as the degree of crosslinking. As the amount of the crosslinkable aromatic monomer used increases and the degree of crosslinking increases, the amount of ion exchange groups introduced into the resulting anion exchange resin tends to decrease. Tends to be less effective, and the crushing strength of the anion exchange resin particles tends to be low.
In the latter stage (b) haloalkylation step, a post-crosslinking reaction can be used as a side reaction of haloalkylation for adjusting the degree of crosslinking.

  The copolymerization reaction of the monovinyl aromatic monomer and the crosslinkable aromatic monomer can be performed based on a known technique using a radical polymerization initiator.

  As the radical polymerization initiator, one or more of dibenzoyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, azobisisobutyronitrile and the like are used, and the amount used is usually monovinyl aromatic. It is 0.05 weight% or more and 5 weight% or less with respect to the weight of the mixture of a monomer and a crosslinkable aromatic monomer.

  As the porosifying agent, it dissolves in the monomer mixture, but the obtained cross-linked copolymer does not swell (hereinafter sometimes referred to as “poor solvent”), or is dissolved in the monomer mixture. A substance that swells the resulting crosslinked copolymer (hereinafter sometimes referred to as “good solvent”) can be used.

  Specifically, a water-insoluble organic compound can be used as the poor solvent. Examples of the water-insoluble organic compound include linear or branched hydrocarbons, linear or branched water-insoluble alcohols, polymers and copolymers. Examples of linear or branched hydrocarbons include pentane, hexane, heptane, octane, nonane, decane, dodecane, isooctane, gasoline, mineral oil, and the like. Examples of water-insoluble alcohols include alcohols having 4 or more carbon atoms and linear or branched alkyl chains, such as n-butanol, s-butanol, t-butanol, pentanol, hexanol, and octanol. And methyl isobutyl carbinol. Examples of the polymer include polystyrene, polyethylene, polypropylene, polyester, polyurethane and the like. Block copolymers can also be used. These may be used alone or in combination of two or more.

  Specific examples of the good solvent include aromatic hydrocarbons such as toluene, xylene (ortho, meta, para), benzene, chlorobenzene, dichlorobenzene, nitrobenzene, bromobenzene, aniline, ethylbenzene, and diethylbenzene. Aromatic hydrocarbons in which the aromatic ring may be substituted can be used. In addition, halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane, and the like can be used. These may be used alone or in combination of two or more.

  As the porous agent in the production of the strongly basic anion exchange resin of the present invention, the use of the poor solvent may be operability during the reaction, separation between the porous agent after the reaction and the crosslinked copolymer, etc. Is preferable. Among the poor solvents, linear or branched hydrocarbons are particularly preferable, and hexane, heptane, and octanes are particularly preferable.

  The porosifying agent is usually 1% by weight or more and 100% by weight or less, preferably 5% by weight or more and 80% by weight or less, more preferably 10% by weight, based on the mixture of the monovinyl aromatic monomer and the crosslinkable aromatic monomer. It is used in an amount of 60% by weight or less. If the amount of the porosifying agent is large, an excessively porous polymer tends to be generated and the crushing strength tends to be lowered. If the amount of the porosifying agent is too small, the amount of polystyrenesulfonic acid adsorbed does not increase. There is a tendency. That is, in the production of the strongly basic anion exchange resin of the present invention, a porosifying agent that is not used in the production of the gel type anion exchange resin is used in the production of a normal porous type anion exchange resin. A gel-type anion exchange resin is produced in which the amount of polystyrene sulfonic acid adsorbed is increased by using less than the amount of the porous agent used.

  In general, in the production of a porous anion exchange resin, as described in Example 1 and Example 2 of Japanese Patent Publication No. 37-13792, a mixture of a monovinyl aromatic monomer and a crosslinkable aromatic monomer is used. When the amount of the crosslinkable aromatic monomer used is higher than 12% by weight, the porosifying agent is used in an amount of 50% by weight or more based on the mixture of the monovinyl aromatic monomer and the crosslinkable aromatic monomer.

  In the production of the strongly basic anion exchange resin of the present invention, when the use amount of the crosslinkable aromatic monomer to the mixture of the monovinyl aromatic monomer and the crosslinkable aromatic monomer is 12% by weight or less, the use of the porosifying agent is used. The amount is preferably 50% by weight or less based on the mixture of the monovinyl aromatic monomer and the crosslinkable aromatic monomer. Further, when the use amount of the crosslinkable aromatic monomer to the mixture of the monovinyl aromatic monomer and the crosslinkable aromatic monomer is 10% by weight or less, the use amount of the porosifying agent is changed between the monovinyl aromatic monomer and the crosslinkable aromatic monomer. The amount is preferably 60% by weight or less based on the mixture. In addition, when the amount of the crosslinkable aromatic monomer used in the mixture of the monovinyl aromatic monomer and the crosslinkable aromatic monomer is 8% by weight or less, the amount of the porous agent used is that of the monovinyl aromatic monomer and the crosslinkable aromatic monomer. It is preferable that it is 70 weight% or less with respect to a mixture. The amount of the crosslinkable aromatic monomer and the amount of the porous agent used for the mixture of the monovinyl aromatic monomer and the crosslinkable aromatic monomer are within a range where a gel-type anion exchange resin having an increased polystyrenesulfonic acid adsorption amount can be obtained. Therefore, it is necessary to set an optimum range so that an anion exchange resin satisfying the strength required for handling in the subsequent process can be obtained.

  The polymerization mode of the strongly basic anion exchange resin of the present invention is not particularly limited, and polymerization can be carried out in various modes such as solution polymerization, emulsion polymerization, suspension polymerization, etc. A suspension polymerization method for obtaining a particulate copolymer is preferably employed. The suspension polymerization method can be carried out by selecting a known reaction condition using a solvent, a dispersion stabilizer or the like generally used for the production of this type of copolymer.

  The polymerization temperature is usually room temperature (about 18 ° C. to 25 ° C.) or higher, preferably 40 ° C. or higher, more preferably 70 ° C. or higher, and usually 250 ° C. or lower, preferably 150 ° C. or lower, more preferably 140 ° C. It is as follows. If the polymerization temperature is too high, depolymerization occurs at the same time, and the degree of polymerization completion tends to decrease. If the polymerization temperature is too low, the degree of polymerization completion tends to be insufficient.

The polymerization atmosphere can be carried out under air or under an inert gas, and nitrogen, carbon dioxide, argon or the like can be used as the inert gas. Moreover, the polymerization method described in JP-A-2006-328290 can also be suitably used. Moreover, the well-known method of obtaining the crosslinked copolymer of a uniform particle size can also be used conveniently. For example, methods disclosed in JP 2002-35560 A, JP 2001-294602 A, JP 57-102905 A, and JP 3-249931 A can be suitably used.
The aforementioned porosifying agent is removed from the reaction system by washing with a solvent or heating distillation after completion of the polymerization reaction to obtain a crosslinked copolymer.

  (B) The haloalkylation step is a step in which (a) the crosslinked copolymer obtained in the polymerization step is swelled and reacted with a haloalkylating agent in the presence of a Friedel-Crafts reaction catalyst to haloalkylate. .

  In order to swell the crosslinked copolymer, a swelling solvent such as dichloroethane can be used. Moreover, depending on the kind of haloalkylating agent, it can be swollen only with the haloalkylating agent.

  Examples of the haloalkylating agent include halogen compounds such as chloromethyl methyl ether, methylene chloride, bis (chloromethyl) ether, vinyl chloride, bis (chloromethyl) benzene, and these may be used alone. Two or more kinds may be mixed and used, but chloromethyl methyl ether is more preferable.

  The amount of the haloalkylating agent used is selected from a wide range depending on the degree of crosslinking of the crosslinked copolymer and other conditions, but is preferably an amount that at least sufficiently swells the crosslinked copolymer. It is 1 weight times or more, preferably 2 weight times or more, usually 20 weight times or less, preferably 10 weight times or less.

  Examples of Friedel-Crafts reaction catalysts include Lewis acid catalysts such as zinc chloride, iron (III) chloride, tin (IV) chloride, and aluminum chloride. These catalysts may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The amount of the Friedel-Crafts reaction catalyst is usually 0.001 to 10 times, preferably 0.1 to 2 times, more preferably 0.2 to 1 with respect to the weight of the crosslinked copolymer. Double the amount.

  The reaction temperature varies depending on the type of Friedel-Crafts reaction catalyst to be employed, but is usually 0 ° C. or higher and preferably 55 ° C. or lower.

  By performing the haloalkylation reaction, a haloalkylated crosslinked copolymer can be obtained.

  (C) In the amination step, the haloalkylated crosslinked copolymer obtained in (b) is reacted with an amine compound to introduce an amino group to produce an anion exchange resin. Can also be carried out using known methods.

  For example, a method in which a haloalkylated cross-linked copolymer is suspended in a solvent and reacted with an amine compound such as trimethylamine or dimethylethanolamine can be mentioned. Here, a trimethylammonium group is introduced by reacting with trimethylamine, and a dimethylethanolammonium group is introduced by reacting with trimethylamine. As a solvent used in these amino group introduction reactions, for example, one kind of water, toluene, dioxane, dimethylformamide, dichloroethane and the like can be used alone or in admixture of two or more kinds. After the amination step, an anion exchange resin can be obtained by changing the salt form into various anion forms by a known method. As the salt form, Cl form, OH form, carbonic acid form, sulfuric acid form and the like are used.

<Treatment of strongly basic anion exchange resin>
The strongly basic anion exchange resin of the present invention is heat-treated in the presence of an alkaline aqueous solution and contains 50% by weight or more of a water-soluble organic solvent (hereinafter sometimes referred to as “organic solvent cleaning solution”). )) Is effective for the characteristics of the strongly basic anion exchange resin of the present invention, which is low elution, has a high ion exchange capacity per volume, and has excellent cycle strength. It is preferable in demonstrating.

  Hereinafter, the treatment of this strongly basic anion exchange resin will be described.

(Heat treatment in the presence of alkaline aqueous solution)
The alkaline aqueous solution used in the present invention is not limited as long as it has an ability to reduce extra strong basic components not incorporated in the resin skeleton of the strong basic anion exchange resin. preferable. The alkali is preferably an alkali metal hydroxide. For example, 1 type (s) or 2 or more types, such as sodium hydroxide, lithium hydroxide, potassium hydroxide, are mentioned. From an economical viewpoint, sodium hydroxide is preferably used.

  The solvent of the alkaline aqueous solution is usually water, but may be a mixed solution of water and alcohol. As the alcohol, alcohol having 1 to 3 carbon atoms, for example, methanol, ethanol, isopropyl alcohol and the like can be used, but methanol is preferable. When the solvent of the alkaline aqueous solution is a mixed solution of water and alcohol, the content of water in the solvent is usually 70% by weight or more, preferably 90% by weight or more.

  Further, the alkali concentration in the alkaline aqueous solution is not particularly limited, but it is usually preferably 1% by weight or more and 12% by weight or less.

  The heat treatment conditions vary depending on the concentration of the alkaline aqueous solution, the amount of the alkaline aqueous solution relative to the amount of the strongly basic anion exchange resin, etc., but the heating temperature usually needs to be 60 ° C. or higher. A high temperature of 80 ° C. or higher, more preferably 90 ° C. or higher is suitable. On the other hand, the upper limit of the heat treatment temperature is 120 ° C. or less.

  About heat processing time, if it is high temperature and high concentration, it can be performed in a comparatively short time. For example, when the heating temperature is 90 to 110 ° C., the treatment may be performed for 4 to 18 hours.

  Examples of the heat treatment method include a column method in which a strong basic anion exchange resin is filled in a column and an alkaline aqueous solution is passed, and a batch method in which a strong basic anion exchange resin and an alkaline aqueous solution are placed in a container and stirred. Can be mentioned.

  In this case, the required amount of the alkaline aqueous solution is usually equal to or greater than the amount of the strongly basic anion exchange resin to be treated (1 BV) as a volume, and there is no upper limit, but the amount is limited to a single treatment amount. Therefore, it is generally 3 times (3 BV) or less the amount of strongly basic anion exchange resin.

(Cleaning process)
A strongly basic anion exchange resin that has been heat-treated in the presence of an alkaline aqueous solution removes a TOC component that desorbs from the strongly basic anion-exchange resin when heat-treated in the presence of an alkaline aqueous solution. Wash with a solution containing 50% by weight or more.

  Although only the heat treatment in the presence of an alkaline aqueous solution reduces the excessive strong base component that is not incorporated in the resin skeleton of the strongly basic anion exchange resin, which causes TOC elution, the desorbed TOC component is: It may not be effectively removed only by washing with ultrapure water, for example, because of its strong affinity with a strongly basic anion exchange resin. Moreover, it is possible to effectively remove the TOC component derived from the styrene skeleton present in the strongly basic anion exchange resin only by contacting with a water-soluble solvent such as methanol. Since extra strong base components that are not incorporated into the skeleton are preserved, the TOC components are not less dissolved from the resin over time.

Prior to this washing treatment, it is desirable to remove the alkaline aqueous solution from the strongly basic anion exchange resin. As the method, it is desirable in terms of efficiency to fill a column with a strongly basic anion exchange resin heat-treated with an alkaline aqueous solution and an alkaline aqueous solution and wash with water. It is desirable that the water quality usually required for washing with water is at least demineralized water. The washing amount is usually 2 BV or more, preferably 4 BV or more. The flow rate is usually SV 0.5 to 2.0 hr ⁻¹ .

  The water-soluble organic solvent used for the cleaning treatment refers to an organic solvent that can be mixed at an arbitrary ratio of water. For example, alcohols having 1 to 6 carbon atoms such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, and hexyl alcohol, acetone and the like can be exemplified, but methanol is preferred. Two or more water-soluble organic solvents can be used in combination.

  The organic solvent cleaning liquid may be a water-soluble organic solvent or an aqueous solution of the water-soluble organic solvent. The aqueous solution of the water-soluble organic solvent is water-soluble in order to efficiently remove the TOC component. The concentration of the organic solvent is preferably higher, and the concentration of the water-soluble organic solvent in the organic solvent cleaning liquid is preferably 50% by weight or more, more preferably 70% by weight or more, and further preferably 90% by weight or more.

  The cleaning method using an organic solvent cleaning solution is a column method in which a strong basic anion exchange resin is filled in a column and the organic solvent cleaning solution is passed, or a strong basic anion exchange resin and an organic solvent cleaning solution are placed in a container and stirred. A batch method is mentioned. From the viewpoint of washing efficiency, the column method is suitable.

When the column method is used, the amount of the organic solvent cleaning liquid is preferably 1 BV or more with respect to the amount of the strongly basic anion exchange resin packed. The filling of the strong basic anion exchange resin is usually carried out using water, but at least the amount equivalent to the strong basic anion exchange resin is required to replace the column system with the organic solvent cleaning liquid. 2 BV or more is preferable. Although there is no restriction | limiting in the upper limit of the organic solvent washing | cleaning liquid amount, Usually, it is 10 BV or less. SV 0.5 to 2.0 hr ^-1 is usually appropriate for the flow rate of the organic solvent cleaning liquid. After the washing with the organic solvent washing liquid, in order to replace the strongly basic anion exchange resin with water, the ultrapure water is continuously charged in a state where the column is packed, and the water flow rate is 10 to 50 BV within the range of the flow rate SV1 to 10 hr ^−1. It is preferable to pass the water.

  When using the batch method, it is preferable to replace the organic solvent cleaning solution in the same amount as the strongly basic anion exchange resin at least twice by increasing the replacement efficiency by removing the attached water (draining state). is there. In addition, in order to replace the strongly basic anion exchange resin with water after washing with the organic solvent washing liquid, the supercapacitor having the same capacity as the amount of the strongly basic anion exchange resin is removed with the attached organic solvent washing liquid removed. It is appropriate to exchange 20 to 100 times with pure water.

[Ultrapure water production equipment]
An ultrapure water production apparatus normally includes an anion exchange resin and a cation exchange resin as ion exchange resins in order to highly remove cations and anions in raw water. In the ultrapure water production apparatus of the present invention, the strongly basic anion exchange resin of the present invention is preferably used in the ultrapure water production apparatus together with the strong acid cation exchange resin, for example, the ultrapure water of the present invention. Examples of the model of the manufacturing apparatus include the following.
(1) Ultrapure water production apparatus equipped with a single-column, multi-bed ion exchange tower in which a strongly basic anion exchange resin layer and a strongly acidic cation exchange resin layer are formed in the same tower (2) Strongly basic Multi-bed ultrapure water production system (3) with an anion exchange column filled with an anion exchange resin and a cation exchange column filled with a strong acid cation exchange resin (3) Strongly basic anion exchange resin and strong acid Mixed bed type ultrapure water production apparatus provided with mixed bed type ion exchange tower mixed and filled with cation exchange resin (4) Combination of (1) to (3) above

  Examples of the strongly acidic cation exchange resin used in combination with the strongly basic anion exchange resin of the present invention include gel type and porous (porous) type strongly acidic cation exchange resins. Preferably, a strong acid cation exchange resin having high oxidation resistance and a high degree of crosslinking is used, and the degree of crosslinking is preferably 8 to 20% by weight, more preferably 12 to 16% by weight. The Within the above range, when the cross-linking degree of the strong acid cation exchange resin is not less than the lower limit value, the elution amount of the eluate from the strong acid cation exchange resin tends to be reduced. In the present invention, the strongly acidic cation exchange resin to be used is not particularly limited, but usually a strongly acidic cation exchange resin having a sulfonic acid group as an exchange group is used.

  The ratio of the use of these strongly acidic cation exchange resins and the strongly basic anion exchange resin of the present invention is the same as that of the production of ultrapure water. The volume ratio is preferably 1: 5 to 5: 1, particularly 1: 3 to 3: 1.

  The strong base anion exchange resin of the present invention is particularly suitable for use in a mixed bed form with a strong acidic cation exchange resin because of its excellent polystyrene sulfonic acid adsorption performance. However, in the present invention, the strongly basic anion exchange resin of the present invention is not limited to use in a mixed bed form with a strongly acidic cation exchange resin, but can be used alone or in combination with other catalyst resins. Can be used in form. In addition, when using the strongly basic anion exchange resin and the strongly acidic cation exchange resin of the present invention in a double bed type, the strongly basic anion exchange resin layer of the present invention is provided in the subsequent stage of the strongly acidic cation exchange resin. It is preferable to adsorb and remove the eluate from the strongly acidic cation exchange resin with the strongly basic anion exchange resin layer.

[Production method of ultrapure water]
The method for producing ultrapure water of the present invention can be carried out in accordance with a conventional method except that the ultrapure water production apparatus of the present invention as described above is used as the ultrapure water production apparatus.
The method for producing ultrapure water according to the present invention is suitable as a method for producing ultrapure water by applying the above ultrapure water production apparatus according to the present invention to a secondary system of a process for producing ultrapure water. The embodiment is not particularly limited as long as it is an ultrapure water apparatus provided with an ion exchange resin tower. For example, the ultrapure water production apparatus of the present invention described above is applied to a primary system of a production process of ultrapure water. Thus, primary pure water can also be produced.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

  The measuring method of various physical properties of the strongly basic anion exchange resin in the following examples is as follows.

<Measuring method of average particle diameter>
The average particle size is Diaion (registered trademark) (ion exchange resin / synthetic adsorbent manual 1) revised edition 4th edition (issued February 26, 2010), No. 140 edited by Mitsubishi Chemical Corporation Ion Exchange Resin Division. It was calculated by the method described on page 142.

<Method for measuring moisture content>
The moisture content is the third edition of the Diaion (registered trademark) (Ion Exchange Resin / Synthetic Adsorbent Manual 1) Revised Edition, 3rd edition (issued February 26, 2010) edited by the Mitsubishi Chemical Corporation Ion Exchange Resin Division. Measured by the method described on page 132.

<Method for measuring neutral salt decomposition ability>
Neutral salt decomposition capacity is the third edition of the 4th edition of Diaion (registered trademark) (Ion Exchange Resin / Synthetic Adsorbent Manual 1) edited by the Mitsubishi Chemical Corporation Ion Exchange Resin Division (issued February 26, 2010) ) Measured by the method described on pages 135-137.

<Measurement method of polystyrene sulfonic acid adsorption amount>
Tosoh Organic Chemical Co., Ltd. polystyrene sodium sulfonate “Polynas PS-1” is passed through a strongly acidic cation resin to form H, and then water is added to dilute to 0.01 mmol / L as H concentration. Thus, a polystyrene sulfonic acid aqueous solution whose concentration was adjusted was prepared.
After treating the strongly basic anion exchange resin with aqueous sodium hydroxide to adjust the salt form to OH form, tap method (put the resin in a graduated cylinder with water, tap the bottom, 10 mL of the resin was collected in a state in which the volume was read in a state where it did not sink, and the column was packed, and then washed thoroughly with water until the organic elution component derived from the resin disappeared.
Subsequently, the polystyrene sulfonic acid solution whose concentration was adjusted was passed through SV (space velocity) = 20 hr ⁻¹ , the absorbance of the polystyrene sulfonic acid solution eluted with a UV detector (225 nm) was measured, and a breakthrough curve was recorded. did. The total amount of polystyrene sulfonic acid adsorbed on the strongly basic anion exchange resin by the time when the UV absorbance of the eluted polystyrene sulfonic acid solution reached 50% with respect to the UV absorbance of the polystyrene sulfonic acid solution whose concentration was adjusted. The adsorption amount was calculated as the adsorption amount of polystyrene sulfonic acid.

<Method for measuring specific surface area>
The strongly basic anion exchange resin was dried by heating under reduced pressure under a vacuum of 50 ° C., then the adsorption isotherm (adsorbed gas: krypton) was measured under liquid nitrogen, and the BET plot was calculated to calculate the specific surface area. The specific surface area was measured by using Autosorb 1MP manufactured by Canter Chrome.

<Measurement method of absorbance>
In an ultraviolet / visible (UV-Vis) spectrum measuring apparatus (“UV2400PC” manufactured by Shimadzu Corporation) using an integrating sphere as a detector, a sample (prepared according to the following method and having a particle size of about 600 μm is placed in a cylindrical cell with a screw cap. The adjusted wet base anion exchange resin (Cl form) was densely packed, the reflectance of light having a wavelength of 800 nm was measured, and the absorbance was determined by Kubelka-Munk conversion.
A sample (a strongly strong basic anion exchange resin in a wet state in which the particle size was adjusted to about 600 μm) was prepared by the method described below.
That is, a strongly basic anion exchange resin (Cl form) was passed through a 600 μm sieve to remove the sieve (fine powder), and the residue on the sieve was removed with demineralized water. Next, the particles clogged with a 600 μm sieve were collected in a vat with pressurized water of demineralized water. The collected product was wrapped in a cloth and centrifuged to remove adhering water. Centrifugation was performed for 7 minutes at a cage diameter of 15 cm and a rotational speed of 3000 rpm.
Integrating sphere manufactured by Shimadzu Corporation (detector: photomaru, inner diameter: 60 mmφ, entrance window: 12 (W) × 20 (H) mm, exit window: 12 (W) × 24 (H) mm, photomaru window: 16 mmφ, integral Sphere aperture ratio: about 11%) was used. However, the optical path diameter of ultraviolet / visible light is 4 mm × 6 mm. As the cylindrical cell with a screw cap, a cylindrical cell with a screw cap (manufactured by synthetic quartz glass, optical path length: 5 mm, optical path surface size: 22 mmφ) manufactured by GL Science Inc. was used.
The slit width was 5 nm. The calibration of the apparatus was performed by directly contacting the opening of the integrating sphere with barium sulfate packed in a dedicated holder (one opening 27 mmφ).
The reflectance was measured by placing a sample (a wet basic anion exchange resin in a wet state adjusted to a particle size of about 600 μm (Cl type)) behind the integrating sphere. A black plate was placed on the back of the sample. After the reflectance measurement, Kubelka-Munk conversion was performed with the attached software to determine the absorbance.
Separately, the same cell was filled with barium sulfate (manufactured by Wako Pure Chemicals, Wako Grade 1), and the same measurement was performed. The values were used as the reflectance and absorbance of the cell itself.
A value obtained by subtracting the absorbance of the cell from the absorbance when the cell was filled with the strongly basic anion exchange resin was calculated as the absorbance of the strongly basic anion exchange resin.

<Measurement method of cycle strength>
The cycle test apparatus is filled with 25 mL of a sample (wet strong basic anion exchange resin (Cl form) adjusted to a particle size range of about 425 μm to 850 μm according to the following method), and SV (space velocity) = 30 h ⁻¹ Then, passing through 2N-sulfuric acid (20 minutes) → washing with water (10 minutes) → 2N-NaOH (20 minutes) → washing with water (10 minutes) as one cycle (required 60 minutes) was repeated 100 cycles. With respect to the resin after the test, the appearance index (perfect sphere) was measured.
A sample (a strongly basic anion exchange resin in a wet state adjusted to a particle size of about 425 μm to 850 μm) was prepared by the method shown below.
That is, a strongly basic anion exchange resin (Cl type) was passed through a 850 μm sieve to remove the sieve (large particles) and collect the resin under the sieve. Subsequently, the collected resin was passed through a 425 μm sieve, the under-sieving was removed, and the resin on the 425 μm clogged resin and the resin on the sieve were collected.
In addition, the appearance index (perfect sphere ratio) is measured by observing 1000 grains visually by dispersing the strongly basic anion exchange resin after the test and observing under a microscope. The number of resin particles (perfect spheres) maintaining an equivalent spherical shape was measured, and the ratio in 1000 grains was determined as a percentage.

<Example 1-1>
As monomers, 311 g of styrene and 51 g of divinylbenzene having a purity of 57% by weight (divinylbenzene: 29 g, monovinyl aromatic monomer: 22 g), 181 g of isooctane and 4.91 g of dibenzoyl peroxide (purity 75% by weight, wet product) were used. A monomer phase was obtained by mixing. A 0.13% by weight aqueous solution of polyvinyl alcohol was used as the aqueous phase, and this was mixed with the monomer phase to obtain a monomer suspension. The suspension was reacted at 75 ° C. for 6 hours with stirring, then heated to 80 ° C. and reacted for 3 hours to obtain a copolymer (1).
100 g of the dried product of the copolymer (1) was put in a round bottom flask, and 500 g of chloromethyl methyl ether was added to sufficiently swell the copolymer. Thereafter, 50 g of zinc chloride was added as a Friedel-Crafts reaction catalyst, the temperature of the bath was set to 50 ° C., and the mixture was reacted for 10 hours with stirring to obtain a chloromethylated copolymer (2).
150 g of the wet product of the chloromethylated copolymer (2) (chloromethylated copolymer (2): 140 g) was placed in a round bottom flask, and 319 mL of demineralized water, 256 g of toluene, and 183 mL of 30% by weight trimethylamine aqueous solution were added. The mixture was reacted at 50 ° C. for 8 hours with stirring to obtain a strongly basic anion exchange resin (Cl form) (Sample A). The evaluation results of the obtained strongly basic anion exchange resin are shown in Table-1.

<Comparative Example 1-1>
Table 1 shows the results of the same evaluation as in Example 1-1 for the strongly basic anion exchange resin “IRA400J” manufactured by Dow Chemical Company.

<Comparative Example 1-2>
Table 1 shows the results of the same evaluation as in Example 1-1 for the strongly basic anion exchange resin “A400MB” manufactured by Purolite.

<Example 2-1>
Sample A was processed according to the following procedure with reference to the method described in JP-A-2004-41915 to obtain Sample B.

Treatment (1) 150 mL of sample A was added to a 500 mL glass round bottom flask with a side tube equipped with a Dimroth reflux tube, and 165 mL of 1.6 wt% aqueous sodium hydroxide was added. The flask was placed in an oil bath, and the oil temperature was raised from room temperature to about 105 ° C. over 2 hours so that the temperature inside the flask became 100 ° C. while gently stirring the resin, and this state was maintained for 8 hours. .
Treatment (2) The flask was cooled by cooling and the resin was taken out, filled in a glass column, and washed with demineralized water at a flow rate of SV2hr ^-1 for 1 hour.
Treatment (3) Further, 150 mL of reagent grade methanol was passed through at a flow rate of SV1hr ⁻¹ for 1 hour.
Treatment (4) Subsequently, sample B was obtained by passing ultrapure water at a flow rate of SV2hr ⁻¹ for 8 hours.

  The organic substance elution amount of the strongly basic anion exchange resin of sample B was measured by the method shown below. Table 2 shows the measurement results of the organic substance elution amount.

<Measurement method of organic substance elution amount>
A glass column was filled with 100 mL of a strongly basic anion exchange resin, and after passing 480 mL of 1N NaOH at SV (space velocity) = 4 h ⁻¹ , 300 mL of ultrapure water was passed at the same flow rate (hereinafter, this The operation is sometimes referred to as “conditioning”.)
A strongly basic anion exchange resin after conditioning is filled into an acrylic column, and 2 hours of ultrapure water is passed through with SV20h- ¹ , and the TOC at the outlet of the column is applied to a sea bass TOC meter (Sievers 500RL) manufactured by GE Analytical Instruments. Measured. The column outlet TOC not filled with resin was measured in the same manner, and the difference in organic matter at the column outlet was taken as the organic matter elution amount.

<Comparative Example 2-1>
With respect to “IRA400J” manufactured by Dow Chemical Co., Sample C was obtained by performing the same treatment as in Example 2-1 except that a 4 wt% aqueous sodium hydroxide solution was used for the treatment (1) in Example 2-1. It was. The results of the same evaluation as in Example 2-1 for Sample C are shown in Table 2.

<Comparative Example 2-2>
About "A400MB" made by Purolite, the same process as Comparative Example 2-1 was performed, and Sample D was obtained. The results of the same evaluation as in Example 2-1 for Sample D are shown in Table 2.

<Evaluation of results>
As shown in Table 1, the strongly basic anion exchange resin of Example 1-1 has better cycle strength than the strongly basic anion exchange resins of Comparative Example 1-1 and Comparative Example 1-2. It can be seen that it can withstand long-term use. Further, as shown in Table 2, the strongly basic anion exchange resin of Example 2-1 has a smaller amount of organic matter elution than the strongly basic anion exchange resins of Comparative Example 2-1 and Comparative Example 2-2. It was. For this reason, when ultrapure water is manufactured using the strong base anion exchange resin of Example 1-1 and Example 2-1, it turns out that high purity ultrapure water can be manufactured for a long period of time. .

Claims (8)

In the method for producing ultrapure water using an ultrapure water production apparatus equipped with an anion exchange resin, the anion exchange resin is a gel type, and the polystyrene sulfonic acid adsorption amount measured by the following method is 0.00. A method for producing ultrapure water, characterized in that a strongly basic anion exchange resin having a mean particle size of 300 μm or more and 1000 μm or less is 25 mmoL / L-resin or more.
<Measurement method of polystyrene sulfonic acid adsorption amount>
Polystyrene sulfonic acid “Polynas PS-1” manufactured by Tosoh Organic Chemical Co., Ltd. was passed through a strongly acidic cation exchange resin to form H, and then the polystyrene sulfonic acid adjusted to an H concentration of 0.01 mmol / L. Prepare an aqueous solution.
The column is filled with a strongly basic anion exchange resin that has been adjusted to OH form by treatment with an aqueous sodium hydroxide solution, washed with water, and then passed through a polystyrenesulfonic acid aqueous solution with a concentration adjusted to give polystyrene equivalent to 50% breakthrough. The amount of sulfonic acid adsorbed is determined and taken as the amount of polystyrene sulfonic acid adsorbed by the strongly basic anion exchange resin. ^2. The production of ultrapure water according to claim 1, wherein the anion exchange resin is a strongly basic anion exchange resin having a specific surface area of less than 1 m ² / g measured by a BET adsorption method using krypton as an adsorption gas. Method.   The ultrapure water according to claim 1 or 2, wherein the anion exchange resin is a strongly basic anion exchange resin having an absorbance of 0.10 or more and 0.44 or less determined from a reflectance of light having a wavelength of 800 nm. Production method.   4. The anion exchange resin according to claim 1, wherein the anion exchange resin is heat-treated in the presence of an alkaline aqueous solution and washed with a liquid containing 50% by weight or more of a water-soluble organic solvent. The manufacturing method of the ultrapure water of any one of Claims 1. The ultrapure water production system is an ultrapure water production system of the double bed and a layer of strongly acidic said anion exchange resin and cation exchange resin layer, according to any one of claims 1 to 4 Manufacturing method of ultrapure water. The ultrapure water production system is an ultrapure water production system of mixed bed having a layer comprising a mixture of strongly acidic cation exchange resin and the anion exchange resin, any of claims 1 to 4 1 The manufacturing method of the ultrapure water as described in a term. The method for producing ultrapure water according to any one of claims 1 to 6 , wherein the ultrapure water device is applied to a secondary system of a process for producing ultrapure water. An ultrapure water production apparatus provided with an anion exchange resin, wherein the anion exchange resin is a gel type, and the polystyrenesulfonic acid adsorption amount measured by the following method is 0.25 mmol / L-resin or more. An ultrapure water production apparatus comprising a strongly basic anion exchange resin having an average particle size of 300 μm or more and 1000 μm or less.
<Measurement method of polystyrene sulfonic acid adsorption amount>
Polystyrene sulfonic acid “Polynas PS-1” manufactured by Tosoh Organic Chemical Co., Ltd. was passed through a strongly acidic cation exchange resin to form H, and then the polystyrene sulfonic acid adjusted to an H concentration of 0.01 mmol / L. Prepare an aqueous solution.
The column is filled with a strongly basic anion exchange resin that has been adjusted to OH form by treatment with an aqueous sodium hydroxide solution, washed with water, and then passed through a polystyrenesulfonic acid aqueous solution with a concentration adjusted to give polystyrene equivalent to 50% breakthrough. The amount of sulfonic acid adsorbed is determined and taken as the amount of polystyrene sulfonic acid adsorbed by the strongly basic anion exchange resin.