JPH0568403B2 - - Google Patents

Description

[Detailed description of the invention]

[Field of Application of the Invention] The present invention relates to a method for producing high-purity hydrogen peroxide solution. [Background of the Invention] Hydrogen peroxide is widely used industrially as an oxidizing agent, bleaching agent, disinfectant, disinfectant, etc., and as a polymerization initiator, explosive, fuel, etc. Particularly recently, it has been used heavily as a cleaning agent for silicon wafers, etc. in the electronics industry, and in this industry, high purity is particularly required. In general, hydrogen peroxide is highly pure immediately after it is produced by distillation, etc., but during storage and transportation, the material of the container is corroded and eluted, and in order to ensure safety during transportation, it must be stabilized to prevent decomposition. Due to the addition of agents, various impurities are mixed into the product when it reaches the user. When used as chemicals for the electronic industry, these impurities have various adverse effects on the product, so various purification methods have been studied to remove these impurities. For metal ions such as sodium ions in hydrogen peroxide water, use a cation exchange resin such as Amberlite IR-120B (trade name of Organo Co., Ltd.), which is a polystyrene ion exchange resin with -SOO ₃ H as an exchange group. However, other metal ions and anions cannot be removed by this method. In addition, methods for removing anions include, for example, quaternary ammonium polystyrene resin [e.g., trimethylbenzylammonium hydroxide (styrene-divinylbenzene)].
There is a purification method using (Pol.Pat.50982, US
Pat. 3294488, etc.), but as is well known, hydrogen peroxide foams violently in alkaline conditions, so the operating temperature is low, e.g. 10°C or lower, preferably 0°C.
It is necessary to do the following. On the other hand, operating at low temperatures does not completely eliminate the decomposition of hydrogen peroxide, and the oxygen gas generated by decomposition remains in the purification resin column, significantly reducing the column purification effect or preventing purification at all. Sometimes I let them do it.
Furthermore, if the operating temperature rises, it is naturally expected that hydrogen peroxide will violently decompose and an accident will occur. Anion exchange resins that are less basic than quaternary ammonium polystyrene resins, such as dimethylbenzylamine poly(styrene-divinylbenzene), can also be used for similar purposes, but they must also be operated at low temperatures. There is a drawback. [Object of the Invention] The present invention was made in view of the above-mentioned situation, and an object thereof is to provide a production method that allows hydrogen peroxide of higher purity to be obtained easily and more safely. [Structure of the Invention] The present invention is a method for producing a high-purity hydrogen peroxide solution, which is characterized by purification using a pyridine-based anion exchange resin. The pyridine-based anion exchange resin used in the present invention has the general formula [) as an ion exchange group.

[Chemical formula] (However, R ¹ to ^{R 4} each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms.) Examples include ion exchange resins made of polymers having a pyridyl group or a substituted pyridyl group represented by: . Examples of the polymer having a pyridyl group or a substituted pyridyl group according to the present invention include the formula

〔Example〕

Example 1 Pretreatment of pyridine-based anion exchange resin with hydrogen peroxide solution Pyridine-based anion exchange resin [manufactured by Koei Chemical Co., Ltd.]
50 g of KEX-212] and 50 ml of 35% hydrogen peroxide solution were stirred at various temperatures in a beaker, and changes in the concentration of hydrogen peroxide were measured. However, the processing temperature is 20℃, 40℃,
The temperature was 60℃. The measurement results are shown in Figure 1. As is clear from Figure 1, the pretreatment of the ion exchange resin can be carried out at low temperatures, but it can be done in a shorter time if heated, and the resin after treatment can accelerate the decomposition of hydrogen peroxide. It turns out that there are hardly any. Example 2 Pyridine-based anion exchange resin (2
hydrogen peroxide solution was purified using each of the following anion exchange resins (species) and other anion exchange resins (three types), and the stability and purification effect of hydrogen peroxide were compared. <Method> Add 100 ml of each ion exchange resin to each column (24 mmφ
x 110cm) and used this to purify the hydrogen peroxide solution. The treatment conditions and results are shown in Table 1.

[Table] *Resin floats due to hydrogen peroxide decomposition and normal column purification operation cannot be performed.
As shown in Table 1, purification using strongly basic anion exchange resins is impossible even at low temperatures (5°C);
Also, even with weakly basic anion exchange resins, -N
Amberlite with _two (CH ₃ ) groups as ion exchange groups
In the case of IRA-93, it cannot be used unless it is operated at a low temperature (5°C), but the pyridine-based anion exchange resin of the present invention can be operated at room temperature, and the purification effect is also , and the superiority of purification using the pyridine-based anion exchange resin of the present invention is clear. Example 3 Pyridine-based anion exchange resin pretreated at 60°C for 8 hours according to the method of Example 1 [manufactured by Koei Chemical Co., Ltd.]
KEX-212] was used to investigate its purification effect. <Method> Transfer 100ml of the above ion exchange resin to a column (24mmφ
110 cm), and used to purify hydrogen peroxide solution at 30°C. The measurement results are shown in Table 2.

【table】

[Table] Example 4 Determination of hydrogen peroxide water purification process Pyridine-based anion exchange resin [KEX-212 manufactured by Koei Chemical Co., Ltd.] pretreated in the same manner as in Example 3 and cation exchange resin having -SO ₃ H group as an exchange group [Amberlite IR-200CH] was used to compare the purification effects of hydrogen peroxide water when used separately and when both were used together. <Method> Add 100 ml of each ion exchange resin to each column (24 mmφ
x 110cm) and used this to purify the hydrogen peroxide solution. However, the flow rate is 137ml/
I went with min. The measurement results are shown in Table 3. However, the results were expressed as an increase or decrease in the quality of the raw hydrogen peroxide solution. In addition, when purifying using a pyridine-based anion-exchange resin and a cation-exchange resin together, the case where the pyridine-based anion-exchange resin is used for purification and then the cation-exchange resin is expressed as anion exchange resin → cation exchange resin, and the reverse is expressed as cation exchange resin. Expressed as exchange resin → anion exchange resin.

【table】

〔Effect of the invention〕

As described above, the present invention provides a manufacturing method for easily and safely obtaining a high-purity hydrogen peroxide solution. Whereas water purification had to be carried out at low temperatures in order to suppress the decomposition of hydrogen peroxide, the pyridine-based anion exchange resin used in the present invention can be purified at room temperature or Since it does not accelerate the decomposition of hydrogen peroxide even at higher temperatures, it is very advantageous in terms of safety and equipment, and its purification effect is also superior to that of benzylamine-based anion exchange resins. It is an invention that has a remarkable effect on the industry, and it is a great contribution to the industry.

[Brief explanation of drawings]

FIG. 1 shows the measurement results in Example 1, where the horizontal axis shows the stirring time (hours) and the vertical axis shows the hydrogen peroxide concentration (%). Also ●――●, △――・―
Δ, ×...× represent the results when pretreatment was performed at 60°C, 40°C, and 20°C, respectively.

Claims (1)

[Scope of Claims] 1. A method for producing high-purity hydrogen peroxide solution, which is characterized by purification using a pyridine-based anion exchange resin. 2. The manufacturing method according to claim 1, which uses a pyridine-based anion exchange resin pretreated with a hydrogen peroxide solution. 3 Claim 1 or 2, in which a pyridine-based anion exchange resin and a cation exchange resin are used together
Manufacturing method described in section. 4 Pyridine ^- based anion exchange resin as an ion exchange group is pyridyl represented ^by the general formula: The manufacturing method according to claim 1, 2 or 3, which is an ion exchange resin made of a polymer having a group or a substituted pyridyl group.