Aqueous hydrogen peroxide purification method and purification system

Patent metadata

Field	Value
Publication number	US-11524896-B2
Application number	US-201716341567-A
Country	US
Kind code	B2
Filing date	Sep 19, 2017
Priority date	Oct 20, 2016
Publication date	Dec 13, 2022
Grant date	Dec 13, 2022

Abstract

A purification method for an aqueous hydrogen peroxide solution, includes passing the aqueous hydrogen peroxide solution through a first H-form strong cation exchange resin column 1 , a salt-form strong anion exchange resin column 2 and a second H-form strong cation exchange resin column 3 . An H-form strong cation exchange resin having crosslinking of 6% or less, an H-form strong cation exchange resin having crosslinking of 9% or more, or an H-form strong cation exchange resin produced by steps (a) and (b) is used as an H-form strong cation exchange resin packed in the second H-form strong cation exchange resin column 3 : (a) copolymerizing a monovinyl aromatic monomer with a crosslinkable aromatic monomer having a non-polymerizable impurity content of 3% by weight or less therein using a predetermined amount of a specified radical polymerization initiator at a predetermined polymerization temperature to obtain a crosslinked copolymer; and (b) sulfonating the crosslinked copolymer.

First claim

The invention claimed is:

1. A purification method for an aqueous hydrogen peroxide solution, comprising sequentially contacting the aqueous hydrogen peroxide solution with:
a first H-form strong cation exchange resin, which is an H-form strong cation exchange resin having a degree of crosslinking of 9% or more, to remove cationic metal ion impurities in the aqueous hydrogen peroxide solution and to reduce an elution amount,
a salt-form strong anion exchange resin to remove anionic metallic impurities, a chloride ion and a sulfate ion, and
a second H-form low cation exchange resin, which is an H-form strong cation exchange resin having a degree of crosslinking of 6% or less, to remove TOC eluted from the salt-form strong anion exchange resin.

2. The purification method for an aqueous hydrogen peroxide solution according to claim 1 ,
wherein the second H-form strong cation exchange resin is an H-form strong cation exchange resin produced by the following steps (a) and (b):
(a) a step of copolymerizing a monovinyl aromatic monomer with a crosslinkable aromatic monomer having a non-polymerizable impurity content of 3% by weight or less therein using a radical polymerization initiator at a concentration of 0.05% by weight or more and 5% by weight or less relative to the total weight of the monomers at a polymerization temperature of 70° C. or more and 250° C. or less to obtain a crosslinked copolymer, wherein at least benzoyl peroxide and t-butyl peroxybenzoate are used as the radical polymerization initiator; and
(b) a step of sulfonating the crosslinked copolymer.

3. The purification method for an aqueous hydrogen peroxide solution according to claim 2 ,
wherein the first H-form strong cation exchange resin is an H-form strong cation exchange resin produced by the following steps (a) and (b):
(a) a step of copolymerizing a monovinyl aromatic monomer with a crosslinkable aromatic monomer having a non-polymerizable impurity content of 3% by weight or less therein using a radical polymerization initiator at a concentration of 0.05% by weight or more and 5% by weight or less relative to the total weight of the monomers at a polymerization temperature of 70° C. or more and 250° C. or less to obtain a crosslinked copolymer, wherein at least benzoyl peroxide and t-butyl peroxybenzoate are used as the radical polymerization initiator; and
(b) a step of sulfonating the crosslinked copolymer.

4. The purification method for an aqueous hydrogen peroxide solution according to claim 2 , wherein the salt-form strong anion exchange resin is produced by the following steps (c), (d), (e), (f) and (g):
(c) a step of copolymerizing a monovinyl aromatic monomer with a crosslinkable aromatic monomer to obtain a crosslinked copolymer;
(d) a step of adjusting the polymerization temperature in the step (c) to 18° C. or more and 250° C. or less and setting a crosslinkable aromatic monomer content (purity) in the crosslinkable aromatic monomer at 57% by weight or more so that the content of an eluting compound represented by the chemical formula (I):

wherein Z represents a hydrogen atom or an alkyl group; and 1 represents a natural number;

is 400 μg or less relative to 1 g of the crosslinked copolymer of the monovinyl aromatic monomer and the crosslinkable aromatic monomer;
(e) a step of haloalkylating the crosslinked copolymer having the content of the eluting compound of 400 μg or less relative to 1 g of the crosslinked copolymer using a catalyst for Friedel-Crafts reaction in an amount of 0.001 to 0.7 parts by weight relative to 1 part by weight of the crosslinked copolymer;
(f) a step of washing the haloalkylated crosslinked copolymer with at least one solvent selected from the group consisting of benzene, toluene, xylene, acetone, diethyl ether, methylal, dichloromethane, chloroform, dichloroethane and trichloroethane to remove an eluting compound represented by the chemical formula (II):

wherein X represents a hydrogen atom, a halogen atom or an alkyl group which may be substituted with a halogen atom; Y represents a halogen atom; and m and n each independently represent a natural number;

from the haloalkylated crosslinked polymer; and
(g) a step of reacting an amine compound with the haloalkylated crosslinked polymer from which the eluting compound has been removed.

5. The purification method for an aqueous hydrogen peroxide solution according to claim 1 , wherein at least one of the first H-form strong cation exchange resin, the salt-form strong anion exchange resin and the second H-form strong cation exchange resin is a gel-type resin.

6. The purification method for an aqueous hydrogen peroxide solution according to claim 1 , wherein after the aqueous hydrogen peroxide solution passes through the salt-form strong anion exchange resin, the aqueous hydrogen peroxide solution passes through another salt-form strong anion exchange resin.

7. A purification method for an aqueous hydrogen peroxide solution, comprising sequentially contacting the aqueous hydrogen peroxide solution with:
a first H-form strong cation exchange resin, which is an H-form strong cation exchange resin having a degree of crosslinking of 9% or more, to remove cationic metal ion impurities in the aqueous hydrogen peroxide solution,
a salt-form strong anion exchange resin to remove anionic metallic impurities, a chloride ion and a sulfate ion, and
a second H-form strong cation exchange resin, which is the H-form strong cation exchange resin having the degree of crosslinking of 9% or more, to remove trace amounts of metal ion impurities contained in the salt-form strong anion exchange resin with oxidation resistance.

8. The purification method for an aqueous hydrogen peroxide solution according to claim 7 ,
wherein the second H-form strong cation exchange resin is an H-form strong cation exchange resin produced by the following steps (a) and (b):
(a) a step of copolymerizing a monovinyl aromatic monomer with a crosslinkable aromatic monomer having a non-polymerizable impurity content of 3% by weight or less therein using a radical polymerization initiator at a concentration of 0.05% by weight or more and 5% by weight or less relative to the total weight of the monomers at a polymerization temperature of 70° C. or more and 250° C. or less to obtain a crosslinked copolymer, wherein at least benzoyl peroxide and t-butyl peroxybenzoate are used as the radical polymerization initiator; and
(b) a step of sulfonating the crosslinked copolymer.

9. The purification method for an aqueous hydrogen peroxide solution according to claim 8 , wherein:
the first H-form strong cation exchange resin is an H-form strong cation exchange resin produced by the following steps (a) and (b):
(a) a step of copolymerizing a monovinyl aromatic monomer with a crosslinkable aromatic monomer having a non-polymerizable impurity content of 3% by weight or less therein using a radical polymerization initiator at a concentration of 0.05% or more and 5% by weight or less by weight relative to the total weight of the monomers at a polymerization temperature of 70° C. or more and 250° C. or less to obtain a crosslinked copolymer, wherein at least benzoyl peroxide and t-butyl peroxybenzoate are used as the radical polymerization initiator; and
(b) a step of sulfonating the crosslinked copolymer.

10. The purification method for an aqueous hydrogen peroxide solution according to claim 8 , wherein the salt-form

Assignees

• Kurita Water Ind Ltd

Inventors

• Yokoi Ikunori
• Ide Yoshiaki
• Chuuman Takaaki

Classifications

• C01B15/013 Primary

  Separation; Purification; Concentration · CPC title

• B01J39/20

  obtained by reactions only involving unsaturated carbon-to-carbon bonds · CPC title

• B01J47/028

  with alternately arranged cationic and anionic exchangers · CPC title

• B01J39/05 Primary

  in the strongly acidic form · CPC title

• B01J41/14

  obtained by reactions only involving unsaturated carbon-to-carbon bonds · CPC title