JPS6217006A - Method for stabilizing peroxide of divalent metal - Google Patents

Abstract

PURPOSE:To prevent deterioration of quality of peroxide of divalent metal due to decrease of effective component with the lapse of time by incorporating a phosphorus component to peroxide of a divalent metal using phosphoric acid, condensed phosphoric acid, or their salt. CONSTITUTION:At leat one phosphorus component selected from phosphoric acid, condensed phosphoric acid, or their salts is(are) incorporated into peroxide of a divalent metal. The peroxide of a divalent metal to be used is peroxide of Mg, Ca, Zn, etc. Suitable stabilizer is orthophosphoric acid, pyrophosphoric acid, (tri, tetra)-polyphosphoric acid, (tri, tetra)metaphosphoric acid, or their salts of Li, Na, K, H, NH4, Mg, Ca, Zn, etc. The phosphorus component to be contained in the stabilized peroxide is adjusted to 0.1-15wt% expressed in terms of P2O5.

Description

DETAILED DESCRIPTION OF THE INVENTION - Industrial Application Field The present invention relates to a method for stabilizing divalent metal peroxides. In detail, at least one selected from phosphoric acid, condensed phosphoric acid, or their salts is used in the divalent metal peroxide [By containing a phosphorus component, quality change due to decrease in active ingredients over time is prevented 2 This invention relates to a method for stabilizing valent metal peroxides.

0 Prior Art The degree to which active ingredients are reduced by decomposition of divalent metal peroxides varies depending on the type of divalent metal, and these are often accepted as essential properties of each peroxide. .

Therefore, there are few examples in which stabilizers are used for these peroxides.2For example, in Japanese Patent Publication No. 53-23279, when calcium peroxide is produced from slaked lime and hydrogen peroxide, magnesium salt and sodium silicate are added. It has been shown to help improve stability during storage.

Problems to be Solved by the Invention The tendency of peroxides to lose their active ingredients and deteriorate in quality during storage is not only a serious problem in the industrial use of peroxides.

This also imposes major restrictions on the storage and management of peroxide. The purpose of the present invention is to:

The object of the present invention is to provide a novel stabilization method that improves these drawbacks of conventional peroxides and obtains divalent metal peroxides that change less over time and have stable quality.

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted extensive research and found that a phosphorus component is added to a divalent metal peroxide using phosphoric acid, condensed phosphoric acid, or a salt thereof. The present inventors have discovered that the stability of peroxides over time is significantly improved by containing them, and have completed the present invention.

That is, 1 the present invention is to contain a phosphorus component in a divalent metal peroxide using at least one type selected from phosphoric acid, condensed phosphoric acid, or salts thereof (hereinafter referred to as "stabilizer"). This is a method for stabilizing divalent metal peroxides characterized by the following.

Divalent metal peroxides to be stabilized in carrying out the present invention are divalent metal peroxides such as magnesium, calcium, and zinc, and stabilizers include orthophosphoric acid and birophosphoric acid.

Various phosphoric acids such as (tri,tetra)polyphosphoric acid, (tri,tetra)metaphosphoric acid, and their Li, Na,
Salts such as K, H, NH4, My, Ca, and Zn are used. These stabilizers can be used alone or in combination of several kinds, if necessary.

In the present invention, as a method for incorporating a phosphorus component into peroxide, as in the case where a water-soluble stabilizer is used as a stabilizer, a divalent component generated by the reaction between the stabilizer and peroxide is used. The metal phosphate may be contained in the peroxide, or the metal phosphate may be mixed in the peroxide with a sparingly soluble divalent metal phosphate as a stabilizer. It may be done in a coercive manner. Specific methods for implementing these include 9 For example, adding a stabilizer to the slurry used in the reaction of hydrogen peroxide acting on divalent metal oxides or hydroxides suspended in water to obtain peroxides. In addition to conveniently selecting the addition method or the addition method to the peroxide slurry after the reaction, the commonly used batch method or It can also be carried out by an extremely simple method of mixing the stabilizer using a continuous kneading machine or mixer.

In the present invention, the amount of moisture that should be present during the stabilization treatment varies depending on the type of peroxide and stabilizer, and is not particularly limited.2 Usually, moisture is a combination of peroxide and moisture. 5 to 95% by weight, preferably 10 to 8% by weight based on the sum of
It is carried out in the range of 0% by weight. The presence of moisture is also necessary for uniform dispersion of the stabilizer for peroxides, and if the intervening moisture is extremely low and uniform dispersion is not possible, satisfactory results are expected. I can't.

In the present invention, various conditions such as the temperature for one hour during stabilization treatment are not particularly important requirements for the stabilization effect, so they can be selected from a wide range.
The temperature range is between 0 and 100 (1") to avoid unnecessary decomposition loss of the active ingredient during the stabilization process.

Preferably, it is carried out at 80Co or less.

Regarding the processing time, it is usually carried out within a short period of several seconds to several tens of minutes, and the processing time is not exceeded unless particularly desired.

After the above-mentioned stabilization treatment, a stabilized peroxide containing a phosphorus component in the two compositions can be obtained by drying by a commonly used drying method. The phosphorus component contained in the stabilized peroxide is 0 as P2O3.
．． 1-15. It is desirable to carry out the addition so that the amount is preferably 0.5 to 10% by weight, and if it exceeds this range, the stabilizing effect will be reduced.

The present invention is preferably carried out when the divalent metal peroxide to be stabilized has an average particle size of 100 μm or less, but if desired, it may have a larger particle size. Alternatively, those whose particle size in appearance has been changed by means such as granulation may pose a problem. As a result, the mechanism by which the stability of peroxide is significantly improved over time is not clear, nor is the decomposition mechanism itself by which peroxide loses its active ingredients over time. However, 2
Peroxides produced by the reaction of oxides or hydroxides of valuable metals with hydrogen peroxide, etc.2 are usually obtained as peroxide compositions containing oxides, hydroxides, or water in addition to metal peroxides. , which themselves have relatively high reactivity or surface activity, and when subjected to stabilization treatment, their properties are greatly reduced by containing a phosphorus component. Furthermore, it is presumed that it contributes to stabilization by acting on some factor that is expected to be a cause of degradability.

・Effects of the Invention According to the present invention, the deterioration in quality due to decomposition of peroxide over time, which has been recognized as an essential characteristic of peroxide and has been a major problem when using it, can be greatly improved by an extremely simple method. This not only expands the scope of use of peroxide, but also reduces the constraints and burden of maintaining quality in its storage and management, which is of great industrial significance.

EXAMPLES The present invention will be explained below using examples and comparative examples.
The present invention is not limited to these.

Comparative Example 1 500 mt of a 60% by weight hydrogen peroxide solution was added over 10 minutes to 750 rrLt of slurry in which 300 T of magnesium hydroxide was suspended in water with stirring, and the reaction was carried out for 1 hour while maintaining the temperature at 30 C@. The slurry was filtered and the resulting wet cake was dried at 120 °C with 15% available oxygen.
A magnesium peroxide containing quadruple IIL96 was produced. This peroxide was then left under conditions of 40c and 0.85% relative humidity to perform a stability test. The results are shown in Table-111. In addition, the stability in Table 9 is shown by the residual rate of effective oxygen calculated by the following formula.

Example 1 In Comparative Example 1, 700ml of 6096 hydrogen peroxide solution
85fiffi* for A! I m 15. 15.1% by weight of effective oxygen was added to the slurry in the same manner as in Comparative Example 1, except that it was added to the slurry after 10 minutes.
A magnesium peroxide containing 2.8''ff1ffi% of phosphorus as P2O was prepared.The stability test results of this were as shown in Table 1.

Examples 2 to 5 Same as Comparative Example 1 except that a stabilizer was added to the slurry after the 1 hour reaction was completed, and the peroxide was removed in the furnace after stirring for 5 minutes. By operation, the peroxide after drying becomes P2O5'cO,S~10・0ffi
Magnesium peroxide was prepared to contain % of phosphorous component and tested for stability. The results are shown in Table-1.

Comparative Example 2 A reaction slurry with a wet standard water content of 7696, obtained by reacting calcium hydroxide suspended in water with hydrogen peroxide, was filtered and dried at 120 c' to obtain 16.5 M5 of effective oxygen.
Calcium peroxide containing . Then,
This peroxide was tested for stability under the same conditions as shown in Comparative Example 1.

The results are shown in Table-1.

Examples 6-7 By the same method as Comparative Example 2, except that before filtering the reaction slurry, the addition of stabilizer to the slurry was carried out at 40C and the peroxide filtration was carried out after stirring for 5 minutes. Peroxide after drying is 0.5 to 10.0% by weight as P2O5
The stability test results of calcium peroxide prepared as follows are shown in Table 2-1.

Comparative Example 3 A reaction slurry with a wet basis moisture content of 7096, obtained by reacting zinc hydroxide suspended in water with hydrogen peroxide, was filtered and 1
Zinc peroxide containing 10.2% effective oxygen was produced by drying at 00c'. Next, the stability of this peroxide was tested under the same conditions as in Comparative Example 1, and the results are shown in Table 1.

Examples 8-9 Before filtering 1 reaction slurry in Comparative Example 3:, 2
Add stabilizer to the slurry at 0c0.

After stirring for 5 minutes, peroxide (peroxide after drying was purified using the same method as in Comparative Example 3 except that arsenic filtration was performed)
The stability test results of zinc peroxide prepared to have a concentration of 0.5 to 10.0% by weight as 5 were as shown in Table 2-1.

Comparative Example A reaction slurry with a moisture content of 7,596 on a wet basis obtained by reacting hydrogen peroxide with magnesium oxide suspended in water was filtered, and the resulting wet cake with a moisture content of 5,396 was filtered.
to produce a magnesium peroxide containing 14.1% of available oxygen.

The results of the stability test for this product were as shown in Table-1.

Examples 10 to 13 The same procedure as in Comparative Example 4 was performed except that the wet cake obtained by filtering the 9 reaction slurry in Comparative Example 4 was placed in a kneader, a stabilizer was added, and kneaded for 2 minutes. P2O
Magnesium peroxide was prepared to contain a phosphorus component of 0.5 to 10.0% by weight as No. 11, and its stability was measured.

The results were as shown in Table-1.

Table-1 Nippon Peroxide Co., Ltd.

Claims (4)

[Claims] (1) Stabilization of divalent metal peroxide characterized by containing a phosphorus component in the divalent metal peroxide using at least one selected from phosphoric acid, condensed phosphoric acid, or salts thereof. Method. (2) The method according to claim 1, wherein the divalent metal peroxide is a magnesium peroxide. (3) The method according to claim 1, wherein the divalent metal peroxide is a calcium or zinc peroxide. (4) The method according to any one of claims 1 to 3, wherein the phosphorus component contained in the divalent metal peroxide containing a phosphorus component is 0.1 to 15% by weight as P_2O_5.