JPH08151203A - Purifier for hydrogen peroxide solution and method for purifying hydrogen peroxide solution - Google Patents

Abstract

(57) Abstract: An apparatus and a method for purifying hydrogen peroxide solution using a reverse osmosis membrane, the peroxidation of which does not involve decomposition of hydrogen peroxide solution which causes product loss and safety problems. A purification apparatus for hydrogen water is provided. A device for purifying hydrogen peroxide water using a reverse osmosis membrane, which is a device for purifying hydrogen peroxide water satisfying the following conditions (A) to (C). (A): Having means for supplying crude hydrogen peroxide solution for purification to the reverse osmosis membrane separator (B): Concentrated peroxidation in which purified hydrogen peroxide solution and removed components are concentrated by the reverse osmosis membrane separator A means for obtaining hydrogen water, combining the concentrated hydrogen peroxide solution with the crude hydrogen peroxide solution, and supplying again to the reverse osmosis membrane separation device (C): the concentrated hydrogen peroxide solution is reverse osmosis again Having means to remove transition metals in hydrogen peroxide before feeding to the membrane separator

Description

Detailed Description of the Invention TECHNICAL FIELD OF THE INVENTION

The present invention relates to a hydrogen peroxide water purification apparatus and a hydrogen peroxide water purification method. More specifically, the present invention relates to an apparatus and a method for purifying hydrogen peroxide solution using a reverse osmosis membrane, which is hydrogen peroxide without decomposition of hydrogen peroxide solution which causes product loss and safety problems. The present invention relates to a water purification device and a method for purifying hydrogen peroxide water.

[0002]

2. Description of the Related Art A technique of using a reverse osmosis membrane for highly removing impurities such as all organic carbon and metals in hydrogen peroxide water is known. However, the conventional method has a disadvantage that a part of hydrogen peroxide solution to be purified causes a decomposition reaction, resulting in loss of products and safety problems.

[0003]

In view of the present situation, the problem to be solved by the present invention is a hydrogen peroxide water purification apparatus and a purification method using a reverse osmosis membrane. Another object of the present invention is to provide an apparatus for purifying hydrogen peroxide solution and a method for purifying hydrogen peroxide solution which do not cause decomposition of hydrogen peroxide solution.

[0004]

That is, one of the present inventions is an apparatus for purifying hydrogen peroxide water using a reverse osmosis membrane, which is provided with the following conditions (A) to (C). The present invention relates to a device for purifying hydrogen peroxide water which is satisfactory. (A): Having means for supplying crude hydrogen peroxide solution for purification to the reverse osmosis membrane separator (B): Concentrated peroxidation in which purified hydrogen peroxide solution and removed components are concentrated by the reverse osmosis membrane separator A means for obtaining hydrogen water, combining the concentrated hydrogen peroxide solution with the crude hydrogen peroxide solution, and supplying it again to the reverse osmosis membrane separation device (C): reverse enrichment of the concentrated hydrogen peroxide solution Having means to remove transition metals in hydrogen peroxide before feeding to the membrane separator

The details will be described below.

The purification apparatus of the present invention must have a means for supplying the crude hydrogen peroxide solution (1) to be purified to the reverse osmosis membrane separation apparatus (2). Specific examples of the means include a storage tank (3) for receiving the crude hydrogen peroxide solution (1) and the storage tank (3).
And a reverse flow osmosis membrane separation device (2) and a pump (5) installed in the flow path (4) and the flow path (4). Here, at least a part of these devices generally contains a metal material such as a rust-free steel pipe (stainless steel).

The reverse osmosis membrane separation device (2) has a reverse osmosis membrane and a pressurizing means, and is a device for purifying a liquid by a so-called reverse osmosis membrane method. For example, it is separated by one flat membrane of the reverse osmosis membrane. A so-called flat plate type, a so-called spiral module type in which a reverse osmosis membrane (membrane) and a spacer or netting are superposed and wound in multiple layers can be used. As the reverse osmosis membrane, a polyamide-based reverse osmosis membrane is preferable, which makes it possible to maintain a sufficient removal efficiency for a long period of time. Specific examples of the polyamide-based reverse osmosis membrane include a composite membrane composed of an aromatic crosslinked polyamide-based polymer and a polysulfone-based polymer and / or a polyester-based polymer. Further, as the reverse osmosis membrane, a low pressure and high blocking performance composite membrane is more preferable, which enables extremely high degree of removal of all organic carbon and metals.

The purification apparatus of the present invention obtains a purified hydrogen peroxide solution (6) and a concentrated hydrogen peroxide solution (7) in which the removed components are concentrated by the reverse osmosis membrane separation apparatus (2), and the concentrated hydrogen peroxide is obtained. It is necessary to have a means for combining water with the crude hydrogen peroxide solution and supplying it again to the reverse osmosis membrane separation device.

The above means is achieved by the flow path (8) connecting the reverse osmosis membrane separation device (2) and the storage tank (3).

The refining apparatus of the present invention must have a means for removing the transition metal in hydrogen peroxide before the concentrated hydrogen peroxide solution is supplied to the reverse osmosis membrane separation apparatus again. A specific example of the transition metal removing means is a method using a cation exchange resin, an anion exchange resin or a chelate resin, that is, a packed column (9) packed with at least one of these resins. There are no particular restrictions on the type of resin used and the type of packed column. Examples of the cation exchange resin include strong acid cation exchange resins. Examples of the anion exchange resin include strong basic anion exchange resin and weak basic anion exchange resin. Examples of chelate resins include aminocarboxylic acid type chelate resins and aminophosphoric acid type chelate resins.

The refining method of the present invention uses the above refining apparatus to adjust the concentration of transition metal in concentrated hydrogen peroxide water to 80 weight p.
It is a method for purifying hydrogen peroxide water, which is controlled to be not more than pb, preferably not more than 10 weight parts by weight.

Here, as a method for controlling the concentration of the transition metal in the concentrated hydrogen peroxide water within the above range, for example, a method of adjusting the performance and the filling amount of the resin used in the packed tower (9) can be mentioned. it can.

The above-mentioned transition metal has a catalytic action for promoting the decomposition of hydrogen peroxide, and examples thereof include iron, titanium and platinum.

The greatest feature of the present invention is that (C) transition metal removing means is used. That is, as the purification of the hydrogen peroxide solution is continued, the transition metal contained in the crude hydrogen peroxide solution accumulates in the concentrated hydrogen peroxide solution. Further, a metal component is eluted from the transition metal material such as iron used in the flow path into hydrogen peroxide, and the eluted metal component is accumulated in concentrated hydrogen peroxide water over time. On the other hand, hydrogen peroxide is catalyzed by a transition metal such as iron and promotes decomposition.
Here, the decomposition of hydrogen peroxide is not only accompanied by the problem of product loss, but also extremely problematic from the viewpoint of safety.
The present invention uses (C) a transition metal removing means to remove the transition metal component serving as a catalyst for the decomposition and control the transition metal component in hydrogen peroxide water to a low level, thus alleviating the above problems. It has been resolved to. Further, by bringing the hydrogen peroxide solution obtained from the apparatus of the present invention into contact with the anion exchange resin and the cation exchange resin, a highly pure hydrogen peroxide solution having lower anions and lower metals can be obtained.

[0015]

The present invention will be described below with reference to examples.

Example 1 A storage tank (3) for receiving the crude hydrogen peroxide solution (1) shown in FIG. 1, a storage tank (3) and a reverse osmosis membrane separation device (2) (spiral type low pressure with an area of 0.6 m ² ). A flow path (4) for connecting a polyamide-based reverse osmosis membrane having high blocking performance), a pump (5) installed in the flow path (4), a reverse osmosis membrane separation device (2) and the storage tank. A flow path (7) connecting (3),
(8) An apparatus having a packed tower (9) capable of packing an ion exchange resin or the like in the flow path was used. The pump (5),
The material of the flow path (4), part of the flow path (7) and part of the reverse osmosis membrane separation device (2) is a non-rust steel pipe (stainless steel).
Was used. Further, the packed column was conditioned using 2N hydrochloric acid and pure water. 20 L of H-type cation exchange resin was filled.

A crude hydrogen peroxide solution containing 45 ppm by weight of total organic carbon and 45 ppm by weight of iron (hydrogen peroxide concentration: 30% by weight) was supplied to the above apparatus. The purification treatment was continued for 300 hours at a supply rate of hydrogen peroxide solution to the reverse osmosis membrane separation device (2) of 600 liters / hr. As a result, the total organic carbon content in the purified hydrogen peroxide was 10 weight pp.
m or less, and the concentration of iron in concentrated hydrogen peroxide is 5 to 2
It was maintained at 0 weight ppb. Further, visual observation was carried out through a transparent resin window installed in the storage tank, but generation of bubbles due to decomposition of hydrogen peroxide was not observed during the purification treatment.

Examples 2 to 5 Experiments were carried out using the same apparatus as in Example 1. Various resins and conditioning agents used in the packed column were used as shown in Table 1. Crude hydrogen peroxide solution was supplied to this apparatus and a purification treatment was performed for about 300 hours. The results are shown in Table 1.
~ 2.

[0019]

[Table 1] ------------------ Example 2 Example 3 Filled resin Anion exchange resin Chelate resin 20 l 20 l Conditioning agent 0.5N NaHCO ₃ 2N HCl Pure water Pure water Supply rate to reverse osmosis membrane device (3) l / hr 800 200 Iron concentration in concentrated hydrogen peroxide water wt ppb 3 to 15 2 to 5 Bubbles in storage tank Generation of pure organic hydrogen in pure hydrogen peroxide water wt ppm <10 <10 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−

[0020]

Table 2 ------------------ Example 4 Example 5 Filled resin Cation exchange resin cation Ion-exchange resin, anion-exchange resin and chelate resin 10 l each 10 l Conditioning agent 2N HCl 2N HCl Pure water Pure water Supply rate to reverse osmosis membrane device (3) l / hr 400 100-670 Concentrated hydrogen peroxide solution Iron concentration of wt ppb 5 to 15 5 to 10 Generation of bubbles in storage tank Total organic carbon in pure hydrogen peroxide water wt ppm <10 <10 −−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−

Comparative Example 1 The procedure of Example 1 was repeated except that the packed tower was not filled with anything. After 50 hours, visual observation was performed through a transparent resin window installed in the storage tank, and as a result, generation of bubbles due to decomposition of hydrogen peroxide was observed. The iron concentration in the concentrated hydrogen peroxide solution at this time was 110 wt ppb.

Example 6 5 L of a strongly basic anion exchange resin was packed in a packed column, and 1.
Conditioning was done with 5N NaOH, 0.5N NaHCO ₃ and pure water. Another packed column was filled with 5 L of a strongly acidic cation exchange resin and conditioned with 2N HCl and pure water. Connect two packed towers in series,
When the purified hydrogen peroxide solution obtained in Example 1 was passed through,
Na, Al, Fe in hydrogen peroxide water flowing out from the packed tower
The concentration of metal impurities, such as, is 0.01 weight ppb or less, the concentration of anion impurities such as chlorine ion sulfate is 20 weight ppb, and the total organic carbon concentration is 10 weight ppm or less, which is a very low impurity content. Hydrogen peroxide was obtained.

Comparative Example 2 Example 6 except that the crude hydrogen peroxide solution used in Example 1 was used.
It carried out similarly to. The total organic carbon concentration in the obtained hydrogen peroxide solution was as high as 42 ppm by weight.

[0024]

As described above, according to the present invention, there is provided a hydrogen peroxide water purification apparatus and method using a reverse osmosis membrane, which decomposes hydrogen peroxide water causing loss of products and safety problems. It was possible to provide an apparatus for purifying hydrogen peroxide water and a method for purifying hydrogen peroxide water that does not involve the above.

[Brief description of drawings]

FIG. 1 is an example showing a flow of a hydrogen peroxide water purification apparatus of the present invention.

[Explanation of symbols]

 1 Crude Hydrogen Peroxide Water 2 Reverse Osmosis Membrane Separation Device 3 Storage Tank 4 Flow Path 5 Pump 6 Pure Hydrogen Peroxide Water 7 Concentrated Hydrogen Peroxide Water 8 Flow Path 9 Packing Tower

Claims (4)

[Claims] 1. A device for purifying hydrogen peroxide water using a reverse osmosis membrane, which is a device for purifying hydrogen peroxide water satisfying the following conditions (A) to (C). (A): Having means for supplying crude hydrogen peroxide solution for purification to the reverse osmosis membrane separator (B): Concentrated peroxidation in which purified hydrogen peroxide solution and removed components are concentrated by the reverse osmosis membrane separator A means for obtaining hydrogen water, combining the concentrated hydrogen peroxide solution with the crude hydrogen peroxide solution, and supplying it again to the reverse osmosis membrane separation device (C): reverse enrichment of the concentrated hydrogen peroxide solution Having means to remove transition metals in hydrogen peroxide before feeding to the membrane separator 2. The purifying apparatus according to claim 1, wherein at least one selected from the group consisting of a cation exchange resin, an anion exchange resin and a chelate resin is used for the transition metal removing means. 3. A method for purifying hydrogen peroxide solution, which comprises controlling the concentration of transition metal in concentrated hydrogen peroxide solution to 80 weight ppb or less by using the purifying apparatus according to claim 1. 4. A method for purifying hydrogen peroxide solution, which comprises contacting the hydrogen peroxide solution obtained by the purification method according to claim 3 with an anion exchange resin and a cation exchange resin.