JPH0578104A - Purification of aqueous solution of hydrogen peroxide - Google Patents

Abstract

(57) [Summary] The present invention provides a "phosphoric acid component etc." obtained by water extraction of a reaction solution prepared by a method of producing hydrogen peroxide by an anthraquinone oxidation / reduction method (so-called anthraquinone method). High concentration hydrogen peroxide aqueous solution containing a large amount of "," with specific activated alumina particles (layer)
Hydrogen peroxide capable of removing phosphoric acid components and the like at a high ratio from the high-concentration aqueous solution of hydrogen peroxide without causing decomposition of hydrogen peroxide by contacting at a temperature of ° C for 6 to 500 minutes. It relates to a method for purifying an aqueous solution.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to "phosphoric acid etc." obtained by water extraction of a reaction solution prepared by a method of producing hydrogen peroxide by an anthraquinone oxidation / reduction method (so-called anthraquinone method). A hydrogen peroxide solution containing a large amount of “hydrogen peroxide solution” is brought into contact with specific activated alumina particles at a relatively low temperature for a specific time, and the phosphoric acid component is removed from the hydrogen peroxide solution without substantially decomposing hydrogen peroxide. The present invention relates to a method for purifying an aqueous hydrogen peroxide solution capable of removing a large amount of hydrogen.

[0002]

Description of the Related Art Generally, as a method for producing an aqueous solution of hydrogen peroxide, a reaction liquid prepared by a method of producing hydrogen peroxide by an anthraquinone oxidation / reduction method (so-called anthraquinone method) is extracted with water. The method of obtaining the hydrogen peroxide aqueous solution obtained by the above method is adopted, and in that case, phosphoric acid is often added for various purposes in the above-mentioned production method.

Conventionally, the phosphoric acid component in the hydrogen peroxide aqueous solution,
As a method for removing acid components such as sulfuric acid and acetic acid, for example, as described in JP-B-39-3002, adsorption removal is performed using an ion exchange resin such as Amberlite (manufactured by Organo Corporation). Ion exchange resin method is known, but with this method, acid components such as phosphoric acid can be removed, but the ion exchange resin particles themselves are decomposed by hydrogen peroxide and used for several times of regeneration. There was a problem that it could not be done and it was not practical.

As a method for removing the phosphate ion component in the hydrogen peroxide aqueous solution, the phosphate ion in the hydrogen peroxide aqueous solution is replaced with a calcium compound, a barium compound,
A precipitation method by reacting an alkaline earth metal compound such as a magnesium compound in a basic atmosphere (pH 7 to 8.5) to form a precipitate such as calcium phosphate and removing the precipitate by filtration is disclosed in US Patent No. 366
No. 4812 specification and the like. However, the above-mentioned precipitation method has a problem that hydrogen peroxide is extremely easily decomposed because the reaction solution becomes basic.

JP-B-48-41158 discloses that phosphoric acid is substantially contained for the purpose of stabilizing a hydrogen peroxide solution by removing a trace amount of metal or organic impurities in the hydrogen peroxide solution. An adsorption method is disclosed in which an aqueous solution of hydrogen peroxide, which is not used, is brought into contact with activated alumina at a temperature near room temperature for a short period of time of 1 to 5 minutes to adsorb and remove the trace amount of impurities and to purify the impurities.

However, in the above-mentioned activated alumina adsorption method, there is no specific disclosure about an aqueous hydrogen peroxide solution containing an excessive amount of phosphoric acid component (PO ₄ ), so that it remains used after being used for various purposes described above. When using an aqueous hydrogen peroxide solution containing an excess of phosphoric acid component, it was completely unknown whether the phosphoric acid component could be removed at a high removal rate.

[0008]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention uses a high-concentration aqueous hydrogen peroxide solution containing an excess of phosphoric acid used for the above-mentioned various purposes to effectively remove hydrogen peroxide. It is an object of the present invention to provide an industrial method capable of easily removing a phosphoric acid component (PO ₄ ) from a hydrogen peroxide aqueous solution at a high removal rate without decomposing it physically.

[0009]

According to the present invention, a phosphoric acid component obtained by water extraction of a reaction solution in which hydrogen peroxide is produced by an anthraquinone oxidation / reduction method is extracted in an amount of 50 to 100.
Aqueous hydrogen peroxide solution containing 00 ppm, containing 90% or more of alumina component as Al ₂ O ₃ and having a specific surface area of 100 to 600 m ² / g, and a temperature of 0 to 50 ° C., The present invention relates to a method for purifying an aqueous hydrogen peroxide solution, which comprises contacting for 6 to 500 minutes to remove the phosphoric acid component from the aqueous hydrogen peroxide solution.

The aqueous solution of hydrogen peroxide used in the present invention is obtained by water-extracting a reaction solution in which hydrogen peroxide is produced by an anthraquinone oxidation / reduction method, and if necessary, the organic solution remaining in the extracted solution. Solvents and the like are removed by organic solvent extraction, and the extract is concentrated to obtain hydrogen peroxide, preferably 20 to 80% by weight, particularly 2% by weight.
5 to 75% by weight, and a phosphoric acid component of 5
0 to 10000 ppm, preferably 100 to 1000 p
Any material containing an excess of about pm may be used. Since the purification method of the present invention can be carried out under the adsorption condition with almost no decomposition of hydrogen peroxide, hydrogen peroxide of about 40 to 8 is used.
It can be suitably adopted for removing the phosphoric acid component from the hydrogen peroxide aqueous solution containing a high concentration of 0% by weight.

The above aqueous hydrogen peroxide solution contains a trace amount of metal such as iron, manganese, chromium, sodium, calcium, aluminum or the like or its ion in an amount of 10 ppm or less, preferably about 1 ppm or less, or an organic impurity of 200 ppm or less. , Preferably about 100 ppm or less.

The activated alumina particles used in the purification method of the present invention contain an alumina component as Al ₂ O _{3 in an amount} of 90% or more, preferably 95% by weight, and have a specific surface area of 100 to 600 m ² / g, preferably 120 to 500 m ² / g activated alumina particles, preferably activated γ-alumina particles. The activated alumina particles have a particle size of 3 to 50 mesh, especially 4 to
It is preferably 30 mesh, more preferably about 5 to 20 mesh.

In the activated alumina particles, iron atoms are 0.1 wt% or less, particularly 0.5 wt% or less as Fe ₂ O ₃ , and chromium, copper and nickel atoms are 10 ppm or less, respectively. , And the sodium content is Na ₂
"Activated alumina particles containing almost no alkali component" such that the O content is 0.3% by weight or less, particularly 0.2% by weight or less, and more preferably 0.1% by weight or less causes less decomposition of hydrogen peroxide. The ratio is preferable in order to obtain a high level of adsorptivity of the phosphoric acid component.

If necessary, the activated alumina particles may be washed with water or an aqueous solution of an inorganic acid such as dilute nitric acid, hydrochloric acid or sulfuric acid, particularly a 0.5 to 5% by weight nitric acid aqueous solution to obtain activated alumina particles. It may be the one from which the alkaline component such as the surface of is substantially removed.

Further, the activated alumina particles have a saturated adsorption rate of phosphoric acid component (maximum adsorption amount of phosphoric acid component / activated alumina particles) of 2 to 20% by weight, particularly 3 to 15 at 30 ° C.
%, More preferably 5 to 12% by weight,
The adsorption operation of the phosphoric acid component in a large amount of hydrogen peroxide aqueous solution can be continuously performed for a long time, and the activated alumina particles in the packed bed of the packed tower can be reactivated at appropriate intervals, which is preferable.

In the purification method of the present invention, the activated alumina particles have a packing density of 500 to 1000 g in an adsorption tower for adsorbing and removing a phosphoric acid component and the like from an aqueous hydrogen peroxide solution.
(Activated alumina particles) / liter (capacity of the packed portion of the adsorption tower), particularly preferably about 600 to 900 g / liter, and filled the packed portion of the adsorption tower with the activated alumina particles, and the activated alumina particle packed bed Is preferably formed and used.

In the purification method of the present invention, the above-mentioned aqueous hydrogen peroxide solution and the above-mentioned activated alumina particles are heated at a temperature of 0 to 50 ° C., preferably 5 to 40 ° C. for 6 to 500 minutes, preferably 6 to 200. The phosphoric acid component is adsorbed and removed from the aqueous hydrogen peroxide solution by contacting for about 8 to 100 minutes. In this invention, the decomposition rate of hydrogen peroxide in the aqueous hydrogen peroxide solution tends to decrease as the temperature at the time of adsorption decreases, but the adsorption amount of phosphoric acid on the activated alumina particles is low at a temperature close to 0 ° C. It tends to decrease in the adsorption of.

In the purification method of the present invention, a batch method in which activated alumina particles are dispersed in an aqueous hydrogen peroxide solution at an appropriate ratio and the phosphoric acid component is adsorbed and removed while stirring can be adopted. In this case, the weight ratio of the activated alumina particles to the hydrogen peroxide solution is 1/2 to 1/100,
It is particularly preferably about 1/5 to 1/50.

Further, according to the purification method of the present invention, activated alumina particles are packed in the packing part of the adsorption tower to form a packed bed of activated alumina particles so that the packing density is about 500 to 1000 g / liter. A continuous method of continuously supplying an aqueous hydrogen peroxide solution to the adsorption tower to adsorb and remove the phosphoric acid component can also be adopted, and this continuous means is preferable. In this case, the SV value (1 / Hr: supply amount of aqueous peroxide solution / volume of activated alumina particle layer) was 0.5 to 10,
In particular, it is preferable to set it to about 0.6 to 6, and the time for the aqueous hydrogen peroxide solution to contact with the activated alumina particle layer (residence time of the aqueous hydrogen peroxide solution in the packed bed) is 6 to 120 minutes.
Particularly, it is preferably about 10 to 100 minutes.

In the present invention, the packed column may be of any type, for example, a supply port for the hydrogen peroxide solution and a discharge port for the hydrogen peroxide solution from which phosphoric acid and the like have been removed. It is preferable to use a cylindrical container having both ends at both ends, and the activated alumina particles are packed in the central part of the packed column at an appropriate packed bed height (L). It is preferable that a porous plate is installed at the bottom of the packed bed to support the packed bed of activated alumina particles.

[0021] The packed column, if necessary, may have a size of about 0-4.
Cooling means for cooling the high-temperature hydrogen peroxide solution so that the adsorption can be performed at a low temperature of 0 ° C. (for example, a cooling jacket surrounding the packed tower, cooling provided inside the packed tower on the supply side). Tube etc.) may be installed.

In the present invention, the aqueous hydrogen peroxide solution is preferably used by vertically installing the packed column, and in this case, the aqueous hydrogen peroxide solution is made to flow from the upper part to the lower part of the packed column. Alternatively, it may flow from the lower part to the upper part of the packed column.

In the present invention, the activated alumina particles which have been subjected to the above-mentioned purification and adsorbed phosphoric acid or the like are 0 to 100.
C., particularly 0 to 50.degree. C., with an aqueous solution of caustic soda, caustic potash and other alkali metal hydroxides (about 0.5 to 20% by weight, particularly 1 to 10% by weight), 1 to 5 times, especially 1 to By washing three times and, if necessary, further washing with pure water and / or an aqueous solution of an inorganic acid such as nitric acid (about 0.1 to 10% by weight, particularly 0.5 to 5% by weight). The adsorbed phosphoric acid component can be removed to easily regenerate the adsorption performance, and the adsorbent can be used again for adsorbing the hydrogen peroxide aqueous solution.

[0024]

EXAMPLE In this example, the hydrogen peroxide concentration of the hydrogen peroxide aqueous solution was determined by a titration method using a potassium permanganate solution in accordance with JIS K1463, and the concentration of the phosphoric acid component was determined by absorption by band momolybdophosphoric acid. Photometric method [Analytical Chemistry Handbook (revised second edition) 208 pages, Publisher: Maruzen, Date of issue:
[February 1978]].

Table 1 shows the chemical composition and physical properties of the activated alumina particles used in the following examples. In each of the examples, the activated alumina particles used were obtained by washing with a dilute nitric acid aqueous solution (concentration: 5% by weight).

[0026]

[Table 1]

Reference Example 1 A reaction solution obtained by oxidizing and reducing anthraquinone in the presence of a catalyst to produce hydrogen peroxide is extracted with water containing phosphoric acid to obtain an extract containing hydrogen peroxide. Then, the organic solvent remaining in the extract is removed by organic solvent extraction to purify the extract, and the extract is concentrated to give an aqueous hydrogen peroxide solution [hydrogen peroxide (H ₂ O ₂ ): 60% by weight, phosphoric acid component (PO ₄ ): 442 ppm, other organic / inorganic components: about 200 ppm] were obtained.

Reference Example 2 In the same manner as in Reference Example 1 except that the conditions such as the amount of phosphoric acid used in the water extraction in Reference Example 1 were changed, the concentration of the phosphoric acid component (PO ₄ ) was 354 ppm, and An aqueous hydrogen peroxide solution having a hydrogen oxide (H ₂ O ₂ ) concentration of 60% by weight was prepared.

Reference Example 3 In the water extraction of the reaction solution obtained in Reference Example 1, the phosphoric acid component (PO ₄ ) was prepared in the same manner as in Reference Example 1 except that the conditions such as the amount of phosphoric acid used were changed. An aqueous hydrogen peroxide solution having a concentration of 463 ppm and a hydrogen peroxide (H ₂ O ₂ ) concentration of 60% by weight was prepared.

Reference Example 4 In the water extraction of the reaction solution obtained in Reference Example 1, the phosphoric acid component (PO ₄ ) was prepared in the same manner as in Reference Example 1 except that the conditions such as the amount of phosphoric acid used were changed. An aqueous hydrogen peroxide solution having a concentration of 386 ppm and a hydrogen peroxide (H ₂ O ₂ ) concentration of 60% by weight was prepared.

Reference Example 5 The same as Reference Example 1 except that the conditions such as the amount of phosphoric acid used in the water extraction of the reaction solution obtained in Reference Example 1 were changed, and the conditions for concentrating the extract were partially changed. Hydrogen peroxide (H ₂
An aqueous solution of hydrogen peroxide having a concentration of O ₂ ) of 60% by weight and a concentration of phosphoric acid component (PO ₄ ) of 1740 ppm was prepared.

Examples 1 to 3 As adsorption towers, a hydrogen peroxide aqueous solution supply port is provided at the lower portion, an adsorption treatment aqueous hydrogen peroxide solution outlet is provided at the upper portion, and a cooling jacket is provided on the periphery. , Activated alumina particles (A type: Mizusawa Chemical Industry Co., Ltd.), which consist of a cylindrical container having a length of 400 mm and an inner diameter of about 22 mm, and an average particle diameter of 3 mm and a specific surface area of 180 m ² / g. Co., Ltd., activated alumina R
N, Table 1 shows the general composition. ) Using an adsorption tower in which a packed bed (where a perforated plate having a large number of holes with a hole diameter of 1 mm is installed in the lower part of the packed bed) of which 100 ml is packed with a packed height (L) of 300 mm is formed, And the said adsorption tower was connected to the supply means of hydrogen peroxide aqueous solution, and the collection container of adsorption treatment liquid, and was installed vertically.

The aqueous hydrogen peroxide solution obtained in Reference Example 1 was charged into a packed column in which a packed bed (L: 300 mm) of activated alumina particles having a capacity of 100 ml was formed.
00 ml / hr (Example 1, SV value: 2), 5
00 ml / hr (Example 2, SV value: 5), and 1000 ml / hr (Example 3, SV value:
Adsorption temperature: 30 by supplying each at the supply rate of 10)
C., and residence time: 30 minutes, 12 minutes, and 6 minutes, adsorption of phosphoric acid components and the like is carried out for 10 hours, and phosphoric acid components and the like are adsorbed and removed to obtain purified hydrogen peroxide aqueous solutions, respectively. It was Table 2 shows the analysis results of the hydrogen peroxide aqueous solution.

Example 4 The aqueous hydrogen peroxide solution obtained in Reference Example 2 was used, the activated alumina particles A were replaced with the activated alumina particles B, and the supply amount of the aqueous hydrogen peroxide solution and the SV value are shown in Table 1. Except for the above, a hydrogen peroxide solution purified by adsorbing and removing phosphoric acid and the like was obtained in the same manner as in Example 2. Table 2 shows the analysis results of the purified aqueous hydrogen peroxide solution.

Example 5 In place of the activated alumina particles C, the supply amount of the hydrogen peroxide aqueous solution and the SV value were changed as shown in Table 1,
In the same manner as in Example 4, a purified hydrogen peroxide aqueous solution was obtained by adsorbing and removing the phosphoric acid component and the like. Table 2 shows the analysis results of the hydrogen peroxide aqueous solution.

Examples 6 to 7 Example 2 (activated alumina particles A) and Example 4 (activated alumina) were used, except that the aqueous hydrogen peroxide solution obtained in Reference Example 3 was used and the adsorption temperature was 10 ° C. In the same manner as the particles B), phosphoric acid and the like were adsorbed and removed to obtain purified hydrogen peroxide aqueous solutions. Table 2 shows the analysis results of the hydrogen peroxide aqueous solution.

[0037]

[Table 2]

Example 8 To 39 g of the hydrogen peroxide aqueous solution obtained in Reference Example 4,
2 g of activated alumina particles (A type) similar to those used in Example 1 were added and stirred to disperse the activated alumina particles in an aqueous hydrogen peroxide solution, and at 30 ° C. for 5 hours.
A purified hydrogen peroxide aqueous solution was obtained by adsorption of phosphoric acid and the like. Table 3 shows the analysis results of the aqueous hydrogen peroxide solution.

Examples 9 to 10 Except that 2 g each of activated alumina particles B (Example 9) and activated alumina particles C (Example 10) shown in Table 1 were used as the activated alumina particles. In the same manner, a purified hydrogen peroxide aqueous solution was obtained. Table 3 shows the analysis results of the aqueous hydrogen peroxide solution.

Example 11 Phosphoric acid was prepared in the same manner as in Example 11 except that 40 g of the aqueous hydrogen peroxide solution obtained in Reference Example 5 and activated alumina particles D2 g were used and the adsorption temperature was 40 ° C. Etc. were adsorbed to obtain a purified hydrogen peroxide aqueous solution. Table 3 shows the analysis results of the aqueous hydrogen peroxide solution.

Example 12 The activated alumina particles D adsorbed with the phosphoric acid component and the like used in Example 11 were treated with an aqueous solution of caustic soda (5% by weight).
Wash twice, then wash with pure water, then dilute nitric acid (2
%), And finally purified water to prepare regenerated activated alumina particles D. Except that the regenerated alumina particles D (regenerated D) were used, in the same manner as in Example 11, adsorption of phosphoric acid and the like was performed to obtain a purified hydrogen peroxide aqueous solution. Table 3 shows the analysis results of the aqueous hydrogen peroxide solution.

[0042]

[Table 3]

[0043]

By the purification method of the present invention, the hydrogen peroxide in the aqueous solution containing substantially a large amount of phosphoric acid component obtained from the reaction solution produced by the anthraquinone method is substantially removed. It is possible to effectively adsorb the phosphoric acid component and the like to the activated alumina particles without decomposing into water, and as a result, it is possible to obtain an aqueous hydrogen peroxide solution from which the phosphoric acid component has been efficiently removed.

Front page continuation (72) Inventor Toru Murakami 10 1978, Kogushi, Ube, Yamaguchi Prefecture Ube Industries Ltd. Ube Integrated Works

Claims (1)

[Claims] 1. An aqueous solution of hydrogen peroxide containing 50 to 10000 ppm of a phosphoric acid component obtained by water extraction of a reaction liquid in which hydrogen peroxide is produced by an anthraquinone oxidation / reduction method, and an alumina component of Al ₂ 90% or more of O ₃ is contained and the specific surface area is 100 to 600 m ² /
g of activated alumina particles at a temperature of 0 to 50 ° C.
A method for purifying an aqueous hydrogen peroxide solution, which comprises contacting for about 500 minutes to remove a phosphoric acid component from the aqueous hydrogen peroxide solution.