JPH06238270A - Adsorption or desalinization - Google Patents

Abstract

PURPOSE:To provide an adsorption or a desalination method which can deal with a large amount of a liquid and elutes few impurities from resin by adsorbing or separating electrolytic substances by introducing a liquid into specified anion exchange resin solely or a mixed bed of it with styrene-based anion exchange resin or strongly acidic cation exchange resin. CONSTITUTION:There is prepared a crosslinked polymer which consists of 30-99.5mole% of repeating monomer units represented by the formula I, or II, 0.1-60mole% of a repeating monomer unit represented by the formula III, and 0-60mole% of another repeating monomer unit which is copolymerizable with the monomer defined by any of the formulae I, II, III. Depending on the case that the functional group having the highest mole percentage among the anion exchange groups of the polymer is a primary amino group, or a binary or a tertiary amino group, or a quaternary amino group, a liquid is introduced into either anion exchanger resin solely or a mixed bed of it with styrene-based anion exchange regin or strongly acidic cation exchange resin which have different weakly-basic-group exchange capacities or neutral salt decomposition capacities and thus electrolytic substances are adsorbed and separated.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for adsorbing or separating an electrolyte from an electrolyte solution, that is, a desalting method. Specifically, Cl ⁻ ions existing in the solution, S
Novel separation and purification in which inorganic strong electrolyte, weak electrolyte, and organic electrolyte such as O ₄ ²⁻ ion, HCO ₃ ⁻ ion, and silica ion are brought into contact with a crosslinked copolymer having a polyvinylamine structure to be adsorbed or separated It is about the method. INDUSTRIAL APPLICABILITY The present invention is used not only for general water treatment but also for semiconductor production, nuclear power, thermal power generation, production of pure water for pharmaceuticals and cosmetics, process water, boiler water, reaction solution, desalination of fermentation liquid, waste water. It can be widely used for adsorption treatment of acidic substances, organic compounds, etc.

[0002]

2. Description of the Related Art Up to now, a method for adsorbing or desalting an electrolyte using an anion exchange resin or an anion exchange resin and a cation exchange resin has been known, and many publications, for example, Diaion Manual (Mitsubishi Chemical). Published by Co., Ltd.). However, as the anion exchange resin for adsorption and desalting, a styrene resin is often used from the viewpoint of performance, chemical stability, strength and cost. A trimethylammonium group and a hydroxyethyldimethylammonium group are used as the strongly basic ion exchange group of this resin. For example, Diaion (registered trademark) SA10A, SA21A (all manufactured by Mitsubishi Kasei Co., Ltd.), Amberlite (registered trademark) IRA-40
0, IRA-410, (all manufactured by Rohm & Haas Co.), and the like. In addition, a weakly basic anion exchange resin DIAION (registered trademark) WA30 (manufactured by Mitsubishi Kasei Co., Ltd.) having a skeleton structure of dimethylaminomethylstyrene is also used. However, the polyvinylamine cross-linked copolymer is
A method of using it as an anion exchange resin for adsorption or desalting has not been known.

[0003]

When a conventional styrene type anion exchange resin is used as a desalting resin, there are many problems as described below. Styrene benzyl group of the structural formula of the anion exchange resin _{(-C 6 H 4 CH 2 -} ) , since although a significant part in the unit weight is not at all involved in ion exchange capacity, per unit weight anionic Decrease the exchange capacity. For example,
The content of the cross-linking agent component, which is difficult for the ion exchange groups to bond, is 0%.
Assuming that a styrenic polymer is present, the ion exchange capacity calculated assuming that one ion exchange group (quaternary ammonium methylstyrene type) is bonded per aromatic ring in the structure is 6.2 with tertiary amine type resin
meq / g, quaternary ammonium salt (OH) type 5.2 m
eq / g. Therefore, in an actual ion exchange resin, there is a cross-linking agent portion, and it is technically difficult to introduce two or more exchange groups per aromatic ring. Therefore, the value of this ion exchange capacity is a theoretical value. It can be assumed that it is close to the maximum value. However, this ion exchange capacity value was not satisfactory for the needs of the market.

Styrene-based weakly basic anion exchange resin [DIAION (registered trademark) WA30 (Mitsubishi Kasei Co., Ltd.)
It is considered to be useful as a desalting resin because it has a high regeneration efficiency as a weakly basic resin. However, when used as a resin for desalination, the steady-state conductivity of the treated water is 0.
Since it reaches only ¹ to 1.0 μS · cm ^−1, it is not always satisfactory as a resin for producing pure water. on the other hand,
When a strong basic anion exchange resin is used, the conductivity reaches 0.1 μS · cm ^-1 , but the regeneration efficiency of the resin is low and it is easy to adsorb organic substances that are impurities, so frequent regeneration operations are required. There are problems such as For example, DIAION (registered trademark) SA10A (manufactured by Mitsubishi Kasei Co., Ltd.), which is a typical strongly basic anion exchange resin, is treated with a 1N-NaOH aqueous solution in an amount twice as much as the neutral salt decomposition capacity of the resin. When regenerated, only about 40 to 50% of the neutral salt exchange capacity is regenerated. As a result, there is a problem that the neutral salt decomposing capacity originally possessed is not fully utilized. On the other hand, the so-called type II strong basic resin such as DIAION SA20A has high regeneration efficiency, but has a problem that the resin is easily contaminated because organic substances are easily adsorbed.

It is known that a styrene-based weakly basic anion exchange resin having a dimethylaminomethylstyrene structure has a benzene ring at the α-position of a nitrogen atom, so that the basicity of amine is lowered. For example, the pKa of benzylamine is 9.35, while the pKa of methylamine is
Ka is 10.6. As described above, the styrene-based weakly basic resin having a benzylamine structure as a basic skeleton is presumed to have a low basicity, so that the types of weak electrolytes that can be adsorbed are limited.

During the production of the anion exchange resin,
Since the exchange of chloromethyl groups to amino groups does not proceed completely, some chloromethyl groups remain in the polymer even after amination. As a result, when the resin is used in the OH form, the residual chloromethyl group and the organic chlorine compound converted from it are gradually hydrolyzed, chloride ions leak out, and in some cases, corrosion of the container occurs.

The quaternary ammonium group and the tertiary amino group of the styrene-based anion exchange resin are liable to be eluted by the exchange group being dropped due to dissolved oxygen in the treatment liquid, chemical stability and the like. Therefore, there is a drawback that pure water is difficult to obtain. In particular, when the flow rate of the passing liquid is low, there is a problem that the steady conductivity becomes high because the elution amount per passing amount is large.

The styrene type ion exchange resin has a high crushing strength, but has a problem that the cycle strength is weak. Therefore, if regeneration and regeneration operations are repeated, there is a problem that the resin is crushed and the pressure loss increases.

On the other hand, (meth) acrylic acid ester type and (meth) acrylamide type anion exchange resins have been proposed. However, the biggest problem with these resins is that the ester or amide bonds are susceptible to hydrolysis. In particular, at the time of regeneration, the resin is exposed to an aqueous NaOH solution, so that the bond is likely to be cleaved. Therefore, the range of use of the ion exchange resin composed of the (meth) acrylic acid ester or the (meth) acrylamide ester is limited.

As a method for solving the above-mentioned problems of the styrene-based, (meth) acrylic acid-based, and (meth) acrylamide-based anion exchange resins, H. Tbal et al. Have proposed a polyvinylamine polymer, its production method, and properties as a chelate resin (Eur, Polym, J ..
25, 4, 331-340 1989, Reactiv.
e Polymers, 17.207-217, (19
92), J. Macromol. Sci. (1992)
Etc.). In this proposal, N-vinyl-tertiary-butyl carbamate and divinylbenzene (hereinafter referred to as “DV
B)) or ethylene glycol dimethacrylate (hereinafter abbreviated as “EGDM”) or the like in the presence of heptane or the like to obtain a porous polymer by suspension polymerization, and then hydrolyzed to obtain polyvinyl having a high specific surface area. An amine copolymer is obtained. However, since the obtained polymer has a low hydrolysis rate, the anion exchange capacity is 4.3 meq / g or less. Further, the report of Tbal et al. Only mentions a chelate resin having a primary amino group and a uranium adsorbent for seawater.

[0011]

The gist of the present invention is to have a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II) in an amount of 30 mol% to 99.5 mol%. The repeating unit represented by the general formula (III) has 0.1 to 60 mol% of the repeating unit represented by the formula (III), and has the general formula (I), the general formula (II) and the general formula (III).
A cross-linked polymer having 0 to 60 mol% of a repeating unit derived from another monomer having a double bond copolymerizable with the monomer giving When a functional group having the highest mole fraction (A) among a certain anion exchange group is a primary amino group (that is, in the general formula (I), the units in which the substituents R ¹ and R ² are both hydrogen atoms are The highest molar fraction): The weak base exchange capacity is 8 ~
22 meq / g-dry resin, (B) when the functional group having the highest molar fraction is a secondary or tertiary amino group (that is, at least the substituents R ¹ and R ^{2 in} the general formula (I)). (One has the highest mole fraction of a unit having a methyl group or an ethyl group): its weak base exchange capacity is 3.0 to
When it is 16 meq / g-dry resin, or (C) the functional group having the highest molar fraction is a quaternary ammonium salt (that is, the unit represented by the general formula (II) has the highest molar fraction). Case): Its neutral salt decomposing capacity is 1.5 to 8.5.
The electrolyte is adsorbed or separated by passing the electrolyte solution through the anion exchange resin which is a milliequivalent / g-dry resin alone and a mixed bed of the styrene type anion exchange resin and the strongly acidic cation exchange resin. An adsorption or desalination method characterized by the above.

[0012]

[Chemical 4]

(In the formula, R ¹ and R ² represent a hydrogen atom, a methyl group or an ethyl group)

[0014]

[Chemical 5]

(Wherein R ³ , R ⁴ and R ⁵ each represent a methyl group or an ethyl group, X ⁻ represents a counter ion coordinated with an ammonium group) 30 mol% to 99.5 mol%

[0016]

[Chemical 6]

(In the formula, R ⁶ and R ⁷ each represent a hydrogen atom or a lower alkyl group, and D is an arylene group which may have a substituent, or a divalent group having an oxycarbonyl group or a carbamoyl group in the structure. The present invention will be described in detail below.

The anion exchange resin for desalting of the present invention is, for example, N-vinylformamide (hereinafter abbreviated as "NVF").
It is obtained by copolymerizing with a polymerizable polyethyleneic monomer. As a raw material monomer, NVF is characterized in that the raw material is inexpensive, is easily hydrolyzed, has good copolymerizability with other monomer components, and is a water-soluble monomer. The content of NVF unit is NVF after polymerization.
Since the ion-exchange group is introduced from the origin unit, the amount is 30 to 99.5 mol%, particularly preferably 40 to 95 mol% with respect to all the monomers.

The polyethyleneic monomer is a monomer which gives the structural unit represented by the general formula (III), and includes, for example, DVB,
It is a monomer compound having two or more radically active ethylenically unsaturated double bonds such as divinyltoluene, divinylxylene, poly (meth) acrylate, and poly (meth) acrylamide. The cross-linking agent is an essential component for making the polymer water-insoluble, but an increase in the content of units derived from the cross-linking agent in the polymer causes a decrease in ion exchange capacity. From this viewpoint, the content of the unit derived from the crosslinking agent is 0.1.
Mol% to 40 mol%, more preferably 0.5 mol% to
It is 30 mol%.

For the purpose of imparting various properties, the resin of the present invention may optionally contain, in addition to the above NVF and polyethylene monomers, other monomers copolymerizable therewith,
For example, a styrene derivative, (meth) acrylic acid ester, (meth) acrylamide, acrylonitrile or the like can be added. In the obtained polymer, the content of the units derived from the other monomer is preferably 0 to 40 mol% based on the copolymer.

As the polymerization reaction, any method such as solution polymerization, suspension polymerization, dispersion polymerization and emulsion polymerization can be adopted. In the present invention, the ion exchange resin used is preferably a spherical polymer, and such a spherical polymer can be usually obtained by various suspension polymerization methods. As a substance that can be used as a polymerization bath during suspension polymerization, organic solvents that are sparingly soluble in NVF, for example, aliphatic or aromatic hydrocarbons such as toluene, petroleum ether, and cyclohexane, halogeno compounds such as polychloroalkane, and chlorobenzene are used. Etc. can be used. The ratio of the polymerization bath is usually in the range of 1 to 5 volumes with respect to 1 volume of the NVF phase composed of NVF and a monomer such as a crosslinking agent. As a method for dispersing the NVF phase in the polymerization bath, a continuous dropping method, a batch dropping method, an introduction method such as dropping or jetting a droplet into a solution by a nozzle can be used.

Further, for example, a single solvent such as acetone, 1-propanol, 2-propanol and ethanol, or a mixed solvent such as methanol-1,4-dioxane and methanol-tetrahydrofuran is added as a porosifying agent to the polymerization system. By doing so, it is possible to obtain a crosslinked polymer having a porous structure. The amount used is preferably 0.1 to 200% by weight with respect to the total amount of the monomers. In addition to the above porosifying agent, as a linear polymer that can be used as the porosifying agent, polyvinylpyrrolidone, polyethylene glycol,
It is also possible to use ethyl cellulose or the like.

In the case of a polymer having a porous structure, its preferred physical properties are a specific surface area of 1 to 500 m ² / g and a pore diameter of 0.5 to 500 nm, more preferably 1 to 1
00 nm. The specific surface area and the physical properties of pores in the present invention are those measured by a nitrogen adsorption method, a mercury intrusion method or the like. Although various kinds of polymerization initiators can be used,
Must be soluble in NVF. As such an initiator, for example, a water-soluble azo polymerization initiator such as 2,2-azobis-2-amidinopropane hydrochloride or 4,4-azobis-4-cyanovaleric acid is used, and the amount thereof is a single amount. Generally 0.02% to 5.0% by weight based on the total body weight
Is the range. The polymerization temperature of the polymerization reaction is usually 30 to 1
The temperature is 20 ° C., and the polymerization time is usually in the range of 1 hour to 15 hours.

In order to obtain the polyvinylamine copolymer which is the ion exchange resin used in the present invention, the NVF cross-linked copolymer obtained by the above-mentioned method is treated with, for example, hydrochloric acid, sulfuric acid, sodium hydroxide, It must be hydrolyzed in an aqueous solution of potassium hydroxide. It is preferable that the reaction temperature of the hydrolysis is 50 to 120 ° C. and the reaction time is usually 1 to 10 hours. Under these reaction conditions, the formamide group can be completely hydrolyzed and a polymer having a primary amino group can be obtained.

The alkylation of the primary amine resin may be carried out by a known method. For example, a strong basic resin having a quaternary ammonium group having a polyvinylamine structure can be obtained by thoroughly alkylating a primary amino group with a reagent such as dimethylsulfate, diethylsulfate, methyl halide, ethyl halide, etc. Can be synthesized. Alternatively, a tertiary amine resin-type weakly basic anion exchange resin can be synthesized by a reaction using formic acid-formalin, and further a known method such as reacting an alkyl halide on the tertiary amino group of this resin can be used. The strongly basic anion exchange resin can also be produced by hydrating or ethylating.

In the desalting method of the present invention, various shaped resins such as pulverized products can be used in addition to the spherical polymer. The crushed product may be crushed to a desired size according to a known method after obtaining a lump resin by solution polymerization or the like. The average particle size of the resin is preferably 1 μm to 2 mm. Usually, when used as a carrier for separation, 300
It is preferably in the range of μm to 2 mm. When used as a carrier for analysis, it is preferably in the range of 2 to 30 μm.

The ion exchange capacity of the cross-linked copolymer produced by the above method is, for example, theoretically, the maximum value of the polyvinyl amine-based resin when the unit weight of the cross-linking agent component to which the ion-exchange group is difficult to bond is 0%. When the ion exchange capacity of the OH form is 9.7 meq / g when the ion exchange group is a trimethylammonium group. As a result, as described above, the styrenic resin having the same functional group was 5.2.
Compared with meq / g, the exchange capacity per unit weight is about 1.8 times, so a resin with a high exchange capacity can be obtained.

The ion exchange capacity in the present invention was calculated as the equivalent per dry resin by measuring the weak base exchange capacity according to the method described in Examples. In the present invention,
If the ion exchange resin used is a strongly basic resin, 4
The content rate of the primary ammonium salt (unit of the general formula (II)) is
It is 30 mol% or more with respect to all ion exchange groups, and may be a strong / weak mixed type anion exchange resin.

As the electrolyte capable of ion exchange or adsorption to which the adsorption / desalination method of the present invention is applied, most inorganic or organic strong electrolytes and weak electrolytes can be mentioned. In general, water contains Na ⁺ ions, K ⁺ ions, Mg ²⁺ ions, Fe (I) ions, Fe (II) ions, Cl ⁻ ions, HCO ₃ ⁻ ions, SO ₄ ²⁻ ions, organic compounds and the like. Mixed. Unlike the styrene resin, the polyvinylamine weak base resin used in the present invention has no benzene ring at the α-position of the nitrogen atom of the amino group. The sexuality is high. For example, p of benzylamine
While the Ka is 9.35, the pKa of methylamine is
Is 10.6. From this, as compared with the conventional benzylamine skeleton resin, the resin used in the present invention has an amino group without passing through a benzene ring, and as a result, as a weakly basic anion exchange resin, an ion-exchangeable weak electrolyte is used. pK
The area of a becomes high. That is, when used as a weakly basic anion exchange resin, silicate ions (pKa = 9.
9), hydrogen cyanide (pKa = 9.3) and boric acid (pK)
It is possible to adsorb weak electrolytes such as a = 9.2) and arsenous acid (pKa = 9.1).

When the polyvinylamine crosslinked polymer used in the present invention is a gel type, the molecular weight of the target substance that can be adsorbed is small because the exclusion limit molecular weight is small although it depends on the degree of crosslinking. On the other hand, in the case of a porous polymer, although the exclusion limit molecular weight is large, a substance having a large molecular weight can be adsorbed, though it depends on the porosifying agent to be added.

In the present invention, NaCl, NaNO ₃ , Na ₂
SO ₄ , KCl, KBr, NaHCO ₃ , Na ₂ HPO
_In addition to inorganic electrolytes such as ₃ , amino acids, amino acid derivatives,
Organic carboxylic acids such as oxalic acid, citric acid, phthalic acid, acetic acid, trifluoroacetic acid, benzoic acid and salts thereof, benzenesulfonic acid, trifluoromethanesulfonic acid, sugar-containing carboxylic acids, organic low molecular weight electrolytes such as amino acids and their derivatives Acid saccharides can also be ion-adsorbed and desalted.

Most of the anion exchange resins currently used are mainly composed of styrene polymers. Since the benzyl group, which is its constituent component, is a highly hydrophobic functional group, it has the drawback of easily adsorbing organic substances nonspecifically. For example, in the ordinary water treatment field, the problem of adsorption of organic substances on anion exchange resins has come to the surface with the recent improvement in water quality. Non-specific adsorption of organic matter has become a serious problem not only in the general water treatment field but also in the field of separating and desalting a solution containing an organic substance. On the other hand, the polyvinylamine cross-linked polymer used in the present invention does not contain a benzyl group unlike the above-mentioned styrene-based cross-linked polymer, and the polyvinyl amine cross-linked polymer has a strongly hydrophobic polyethylene chain with a hydrophilic chain. It has a structure in which it is covered with a certain amine and the highly hydrophilic amino group is exposed. Therefore, the polyvinylamine-based polymer is a very hydrophilic crosslinked polymer,
It is suitable for adsorption and desalination because it is difficult to non-specifically adsorb organic substances.

Further, in the present invention, the weakly basic anion exchange resin as described above is used in combination with the strongly basic cation exchange resin. However, the existing styrene-based weakly basic ion exchange resin has a large steady-state conductivity because there are many eluates from the resin. However, the polyvinylamine-based resin used in the present invention is suitable as a desalting method because it has a small steady-state conductivity due to a small amount of eluate.

The present invention is applicable to a wide range of water treatment fields such as simple cartridge type demineralizers, softening of boiler water, pure water production for semiconductor production, and pure water production for (nuclear) power plants. Can be used in. In addition, it can be used for separating and purifying pharmaceuticals. Specifically, a method of incorporating a resin into a part of a multi-tower type device (single bed / single tower type) or a mixed bed, and filling a weakly basic anion exchange resin on the upper part of a strongly basic anion exchange resin There are many methods such as a method using a dual layer method or a batch method.

Since the ion exchange resin used in the desalting method of the present invention is a strongly basic and / or weakly basic anion exchange resin, it is carried out after the acidic resin treatment or in a mixed bed with the acidic resin. Is common. In the present invention, the resin used can be regenerated with a basic aqueous solution such as sodium hydroxide as in the case of an ordinary anion exchange resin. When the weakly basic resin is regenerated, a sodium hydroxide aqueous solution can be used according to a known method, but a weakly basic aqueous solution such as an aqueous ammonia solution or an aqueous sodium carbonate solution can also be used. When a strongly basic aqueous solution such as sodium hydroxide is used, the solution concentration of the regenerated solution is usually 0.05N to 5N. The solution concentration in the case of the aqueous ammonia solution is usually 0.1N to 5N aqueous solution.

Since the weakly basic resin has a high regeneration efficiency, the exchange capacity of the polyvinylamine crosslinked polymer can be fully utilized, and the amount of the regenerant may be small. That is, it can be almost completely regenerated at an amount equivalent to twice the exchange capacity. However, in the case of regeneration with a carbonate, the carbonate ion is partly coordinated to the weak base, so that the steady-state conductivity is higher than in the case of regeneration with sodium hydroxide, and the desalting treatment amount is low, which is not preferable.

The method of regenerating the anion exchange resin depends on the method of filling the resin, and in the case of the dual layer, f
The full counter method, split reproduction, etc. are performed. Since the polyvinylamine-based crosslinked polymer used in the present invention contains no Cl atom at all, Cl ions do not elute from the crosslinked polymer resin, which is preferable because it does not cause problems such as corrosion of the container. .

[0038]

INDUSTRIAL APPLICABILITY As described above, the present invention has a higher electrolyte adsorption capacity than conventional styrenic anion exchange resins, is excellent in regeneration efficiency, and has high hydrophilicity because it does not contain a benzyl group, and therefore nonspecific adsorption is also possible. Since it uses a polyvinylamine resin that is excellent in chemical stability and does not contain organic halogen compounds at all, it has a large treatment amount, and there is no contamination due to the elution of organic substances from the resin. It proposes an adsorption and desalination method applicable to the field.

[0039]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the following examples, meq / g represents milliequivalent per dry resin weight.

Production Example-1 Polymerization Reaction: A 1000 ml 4-necked flask was charged with 400 ml of cyclohexane and 800 mg of ethyl cellulose to prepare a polymerization bath solution. On the other hand, NVF (purity 94%, impurities mainly include formic acid) 180 g, divinylbenzene (purity> 80%) 20.0 g, deionized water 4.5 g, V-5
0 (azo polymerization initiator, trade name, manufactured by Wako Pure Chemical Industries, Ltd.) 4
An NVF solution containing 00 mg was prepared. Both solutions were bubbled with nitrogen (N ₂ ) in advance, and the polymerization reaction was performed under an N ₂ atmosphere (hereinafter, the polymerization reaction was performed under a nitrogen atmosphere). The NVF phase solution prepared above was gradually added dropwise while stirring the cyclohexane solution at 100 rpm. Three
After stirring for 0 minutes, the temperature was raised and polymerization was carried out at 65 ° C. for 8 hours. After the temperature was raised, the NVF phase gelled in about 15 minutes. After completion of the polymerization, the cross-linked copolymer was placed in a Buchner funnel, washed with methanol, and then washed with water. The polymerization yield was 81% based on the raw material monomers. The resulting crosslinked copolymer was white in appearance, but was slightly opaque when observed under a microscope. The degree of swelling of the obtained polymer in demineralized water is 4.63 m.
It was 1 / g and the water content was 68.9%. This polymer was a gel type and had a specific surface area of 0 m ² / g.

Hydrolysis reaction: The above drained crosslinked polymer was placed in a 1 liter flask, and 700 ml of 2N-NaOH aqueous solution was added. The solution was warmed and hydrolyzed at 85 ° C. for 4 hours. After the reaction was completed, the resin was washed with water to give a regenerated form. The degree of swelling of the obtained cross-linked copolymer was 7.33 ml /
The water content was 78.9%. The weak base exchange capacity was 18.0 meq / g and 2.46 meq / ml. ^{From 13} C-NMR (CP-MAS method), the formyl group (164 ppm) was completely disappeared.

Production Example-2 Hydrolysis-Methylation reaction: 100 ml of the drained resin obtained in Production Example-1 and 100 ml of demineralized water were placed in a 500 ml flask, and sodium hydroxide (NaO) was added thereto.
H) 32 g, and the initial NaOH aqueous solution concentration was 5N
In addition, the concentration of the aqueous solution at the end was set to 2.5N. It was hydrolyzed at 85 ° C. for 3 hours. After cooling to 40 ℃,
27 g of formic acid and 81 g of 37% aqueous formaldehyde solution were added. Further, hydrochloric acid was added to adjust the solution to pH 5. The temperature was gradually raised and the reaction was carried out at 90 ° C. for 3 hours.
Carbon dioxide was generated violently in the initial stage, but it almost disappeared at the end of the reaction. After completion of the reaction, the resin was washed with water and then made into an OH type with a 0.1N-NaOH aqueous solution. The polymer obtained by washing the resin again with water had a weak base exchange capacity of 9.3 meq / g and an average particle size of about 340 μm. The methylation degree of the amino group was measured by NMR ( ¹³ C-CP
/ MAS method), the degree of methylation was 1.8. Considering together the results of Production Example-1 described above, it is considered that the anion exchange group contains 80% or more of tertiary amine, and a part thereof remains as primary amine or secondary amine.

Production Example-3 Alkylation reaction: The amino group was methylated using the resin (regenerated form) after hydrolysis obtained in Production Example-1.
Drain the polymer 50 into a 500 ml 4-necked flask.
ml, 150 ml of 50% aqueous methanol solution was added. Into this, 50 ml of an aqueous methanol solution of 30 ml of methyl iodide was added.
An aqueous solution containing ml and 28 g of sodium carbonate was slowly added dropwise. After completion of the reaction, the resin was poured into a Buchner funnel and washed with methanol and demineralized water. The obtained resin had a strong base exchange capacity of 6.3 meq / g, a weak base exchange capacity of 1.9 meq / g, and an average particle size of about 330 μm.

Method for measuring ion exchange capacity: The cross-linked polymer obtained by the above production example and about 15 ml of each DIAION (registered trademark) were packed in a column and 2N-NaOH was used.
500 ml of the aqueous solution was passed through SV (space velocity) 20 and then 1 liter of demineralized water was passed through SV 20. Accurately collecting 10.0 ml of this resin using a graduated cylinder, and filling the column. 250 ml of 4% NaCl aqueous solution was passed through this through SV5, and the eluent was received in a volumetric flask. This solution was titrated with acid and base to measure the strong base exchange capacity. Further, 100 ml of a 1N-HCl aqueous solution is flown at SV10,
The effluent was received in a volumetric flask, and 50 ml of methanol was flown to wash the resin. Further, the liquid remaining in the resin layer was extruded by compressed air to collect these solutions. This solution was titrated with acid and base to measure the weak base exchange capacity. Regarding the exchange capacity per weight, separately, 10.0 ml of OH type resin was drained with a centrifuge to remove attached water, and then the resin was dried at 60 ° C. until a constant weight was reached. The weight of the dry resin was measured and converted into an ion exchange capacity per weight.

Test Resin Samples Cross-linked copolymers obtained in the above Production Example-1, Production Example-2 and Production Example-3 and commercially available Diaion (registered trademark)
SA10A (styrene-based strong base resin), SA20A (styrene-based strong base resin), and WA30 (styrene-based weak base resin) (manufactured by Mitsubishi Kasei Co., Ltd.) were used.

Preparation of Raw Aqueous Solution In 20 liters of demineralized water, 7.02 g of sodium chloride (special grade: manufactured by Kishida Chemical Co., Ltd.) was dissolved to obtain 300 ppm NaCl.
An aqueous solution (calculated as CaCO ₃ ) was prepared.

NaNO ₃ , Na ₂ SO ₄ , CH ₃ COO
300 ppm of Na and NaHCO ₃ (calculated as CaCO ₃ )
Preparation of aqueous solution In 20 liters of demineralized water, 10.18 g of sodium nitrate (special grade: manufactured by Kishida Chemical), 9.96 g of sodium sulfate decahydrate (special grade: manufactured by Kishida Chemical), sodium acetate
Trihydrate (special grade: manufactured by Kishida Chemical) 16.31 g, and sodium hydrogen carbonate (special grade: manufactured by Kishida Chemical) 10.08 g
Were dissolved into 300 ppm (calculated as CaCO ₃ ) solutions.

300 p of oxalic acid, phthalic acid and citric acid
Preparation of pm (CaCO ₃ equivalent) aqueous solution In 20 liters of demineralized water, oxalic acid dihydrate 7.55
g, potassium hydrogen phthalate 12.33 g, and citric acid anhydride (special grade: manufactured by Kishida Chemical Co., Ltd.) 7.67 g are dissolved to obtain 300 p
Each solution of pm (calculated as CaCO ₃ ) was used.

Example 1 Desalination test using mixed bed Diaion (registered trademark) SK1B (regenerated type) (manufactured by Mitsubishi Kasei Co., Ltd.) and three kinds of anion exchange resins (regenerated type) produced in the respective production examples were respectively used. The mixture was mixed and packed in a glass column (column diameter: 13.9 mmφ × about 40 cm). However, in the case of Production Example-1, since the anion exchange resin has a large weak base exchange capacity, 30 ml was used, and SK1B was set to 20 ml, and in the case of the other two resins, 25 ml of each of the production examples was mixed with 25 ml of SK1B. An aqueous NaCl solution (300 ppm: CaCO 3) was added to this column as a raw water preparation solution.
₃ equivalent) was passed through the column at SV = 10 hr ^-1, eluate conductivity cell (Toa Telecommunications Ltd. through cell constant 0.10) was continuously measured conductivity of the eluent.

Table 1 below shows the amount of processing liquid and the steady-state conductivity (μS-cm ^-1 ). The amount of processing liquid is BTP with conductivity.
Is a treatment amount (calculated as CaCO ₃ ) when 0.1 μS / cm. However, Production Example-3 and WA30 are BTP
Of 0.5 μS / cm is shown. g /
1-R represents the treatment amount (g) per liter of resin.

[0051]

[Table 1]

Example 2 Resins of Production Examples 1 and 2 as anion exchange resins and commercially available anion exchange resins DIAION SA10A and WA3.
0 (OH type) 25 ml each and SK as cation exchange resin
25 ml of 1B (H type) was used as a mixed bed, and the mixture was packed in a 13.9 mmφ glass column. However, since the resin of Production Example 1 has a large anion exchange capacity, 20 m of anion exchange resin is used.
1 and SK1B were 30 ml. An aqueous solution in which each electrolyte shown in Table 2 below is dissolved in a column of 300 ppm (CaCO
₃ conversion) was passed through SV10, the treatment of the eluent and the conductivity were measured. The results are shown in Table 2 below.

[0053]

[Table 2]

Example 3 75 ml of DIAION SK1B (H type) was packed in a glass column (column diameter: 20 mmφ × about 35 cm), while resin DIAION SA1 of Production Examples -1, -2 and -3.
0A, SA20A commercially available anion exchange resins (OH
Form) Each 25 ml was packed in a column 13.9 mmφ. First, the SK1B column manufactured in this way
0 ppm (CaCO ₃ equivalent) NaCl aqueous solution was added to SV10
After the solution was passed at hr ^−1, it was passed through the column of each anion exchange resin. As a result, the conductivity BTP was 0.1 μS / cm.
The processing amount and the steady-state electric conductivity μS · cm ⁻¹ are shown in Table 3 below. The amount of processing liquid is 1.0 for BTP of conductivity.
The processing amount (calculated as CaCO ₃ ) when μS / cm is shown.

[0055]

[Table 3]

[0056]

[Reference example]

Regeneration of resin 25 ml each for anion exchange resin (OH type) of the above production example
A large excess of 2N-HCl aqueous solution was passed through the mixture to completely remove Cl.
Shaped The resin was washed with demineralized water. SV5hr ⁻¹ was added to the resin in an amount of 2 times or 4 times the equivalent of an aqueous solution of NaOH, an aqueous solution of Na ₂ CO _{3 and an} aqueous solution of NH ₃ with respect to the decomposition capacity of the neutral salt.
Then, the solution was regenerated. On the other hand, the cation exchange resin SK1B used was completely regenerated with a 2N-HCl aqueous solution. These anion exchange resin and SK1B resin were mixed bed type and packed in a column.

The performance (regeneration efficiency) of the resin after regeneration was measured by a column test, and the steady state conductivity of the treated amount was measured as shown in Table 4 below.
~ Shown in Table-7. In addition, the processing amount was set to 0.
Processing amount when 1 μS / cm (calculated as CaCO ₃ ) However, when reproducing with NH ₃ , BTP is 0.5 μS / cm
cm, when regenerated with Na ₂ CO ₃ , BTP is 1.0
It was set to μS / cm.

[0058]

[Table 4]

[0059]

[Table 5]

[0060]

[Table 6]

[0061]

[Table 7]

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Claims (1)

[Claims] 1. A repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II) are contained in an amount of 30 mol% to 99.5 mol%, and the repeating unit represented by the general formula (III) is Another unit having 0.1 mol% to 60 mol% and having a double bond copolymerizable with the monomers giving the general formula (I), the general formula (II) and the general formula (III). A cross-linked polymer having 0 to 60 mol% of a repeating unit derived from the body, wherein (A) the functional group having the highest molar fraction is 1 among the anion exchange groups which are the functional groups of the polymer.
When it is a ^primary amino group (that is, when the units in which the substituents R ¹ and R ² are both hydrogen atoms in the general formula (I) has the highest mole fraction): its weak base exchange capacity is 8 to 22 meq / g-dry resin, (B) the functional group having the highest molar fraction is a secondary or tertiary amino group (that is, in the general formula (I), at least one of the substituents R ¹ and R ² is methyl). Group or ethyl group has the highest molar fraction): weak base exchange capacity is 3.0 to 16 meq / g-dry resin, or (C) functional group with the highest molar fraction Is a quaternary ammonium salt (that is, the unit represented by the general formula (II) has the highest molar fraction): its neutral salt decomposition capacity is 1.5 to 8.5 meq /
Adsorption or separation of an electrolyte by passing an electrolyte solution through an anion exchange resin which is a g-dry resin alone or a mixed bed of the anion exchange resin and a styrene type anion exchange resin or a strongly acidic cation exchange resin. An adsorption or desalination method characterized by: [Chemical 1] (In the formula, R ¹ and R ² represent a hydrogen atom, a methyl group or an ethyl group). (In the formula, R ³ , R ⁴ and R ⁵ each represent a methyl group or an ethyl group, and X ⁻ represents a counter ion coordinated with an ammonium group). (In the formula, R ⁶ and R ⁷ each represent a hydrogen atom or a lower alkyl group, and D represents an arylene group which may have a substituent or a divalent group having an oxycarbonyl group or a carbamoyl group in the structure. Represent)