TW201302604A - Method for direct production of hydrogen peroxide using brookite type titanium oxide - Google Patents

Abstract

The present invention provides a method for direct production of hydrogen peroxide having a step of reacting hydrogen and oxygen under the presence of a catalyst in which at least one type of active metal selected from the group consisting of platinum, palladium, silver and gold is deposited on a brookite type titanium oxide.

Description

Direct manufacturing method using hydrogen peroxide of brookite-type titanium oxide

The present invention relates to a process for directly reacting hydrogen with oxygen to produce hydrogen peroxide, and more particularly to a process for directly producing hydrogen peroxide using a catalyst comprising brookite-type titanium oxide and a specific active metal.

Since hydrogen peroxide has an oxidizing power and has a strong bleaching and bactericidal action, it is used as a bleaching agent or a bactericide for paper, pulp, fiber, and aquatic products. Further, hydrogen peroxide is an important industrial product widely used in an oxidation reaction including epoxidation and hydroxylation. Further, hydrogen peroxide is used for surface cleaning in the semiconductor industry, chemical polishing of copper, tin, and other copper alloy surfaces, etching of electronic circuits, and the like. Furthermore, hydrogen peroxide is only a water and oxygen even if it decomposes, so it is an important place from the viewpoint of green chemistry, and it is also attracting attention as a substitute for chlorine bleach.

Conventionally, hydrogen peroxide is produced by an organic method, a hydrazine method, an electrolysis method, or the like, and is particularly used as an industrial production method. However, the hydrazine method is composed of multiple stages such as reduction, oxidation, formation of hydrogen peroxide, purification, concentration, etc., which not only has the disadvantage of high equipment investment cost, but also uses a large amount of energy, and The problem of release of organic solvents into the environment such as the atmosphere.

In order to improve such problems, attempts have been made to manufacture methods other than the above-described manufacturing methods, one of which is a method of directly producing hydrogen peroxide from oxygen and hydrogen by using a catalyst in a reaction medium. For example, it has been proposed to use a platinum group metal as a catalyst to produce hydrogen peroxide from oxygen and hydrogen, and it is known that a certain concentration of hydrogen peroxide can be generated (for example, Patent Document 1, Patent Document 2, and Patent). Document 3). The reaction pressure of these methods is all above 2 MPa, and an aqueous solution in which an acid or an inorganic salt is dissolved is used as a reaction medium. In order to suppress the decrease in the selectivity in the reaction, by adding a halogen ion to the reaction medium, The activity of the catalyst is suppressed, the selectivity of the hydrogen peroxide generating reaction is greatly increased, and the concentration of hydrogen peroxide obtained is increased.

Patent Document 4 discloses a method for producing hydrogen peroxide from oxygen and hydrogen under pressure using a platinum group catalyst in an acidic aqueous solution of sulfuric acid, which is selectively produced by allowing a halogen ion such as a bromide ion to coexist in an aqueous solution. High concentration of hydrogen peroxide. That is, in the prior art, a method of producing a high concentration of hydrogen peroxide by reacting oxygen with hydrogen in a reaction medium to produce a high concentration of hydrogen peroxide requires a reaction at a high pressure of 2 MPa or more in order to obtain hydrogen peroxide at a high selectivity. Further, in the method for producing a platinum group metal catalyst using titanium oxide as a support, a high concentration of hydrogen peroxide can be obtained without lowering the selectivity at a low pressure (for example, Patent Document 5). However, this titanium oxide has many small particle diameters, and since the particle shape is easily pulverized, it is difficult to practically use it as an industrial catalyst.

On the other hand, Patent Document 6 discloses a method for producing hydrogen peroxide by carrying out oxygen and hydrogen using an aqueous solution as a reaction medium on a catalyst in which titanium oxide and a platinum group metal are supported on a carrier which is not easily broken. The contact reaction can obtain a high concentration of hydrogen peroxide at a low pressure.

Further, Patent Document 7 describes a method for producing a catalyst in which a titanium-containing silicate porous body is suspended in a solution (a metal salt-containing solution) in which a Pd salt and an Au salt are dissolved, and a suspension is prepared. The obtained suspension was irradiated with ultraviolet rays to cause metal fine particles containing an alloy of Pd and Au to be deposited on the surface of the porous body of titanium-containing silicate. However, this method is a method in which a metal is supported on a suspended catalyst by a photoprecipitation method, and the carrier component is not supported by a good high dispersibility, so that the performance of the catalyst is poor. Furthermore, it takes a very long time to obtain a catalyst, and thus it is not suitable as a method of obtaining a catalyst for the amount necessary for actual production. Further, Patent Document 8 describes a method for improving a catalyst for producing hydrogen peroxide by direct method, in which a catalyst carrier is subjected to acid washing, and gold and/or palladium are appropriately deposited on a washing support at the same time. The catalyst precursor is formed, and then the catalyst precursor is preferably heat-treated at a temperature of 400 ° C or higher to form a catalyst containing gold, palladium or gold and palladium particles. Further, it is described that ceria, titanium oxide, aluminum oxide, iron oxide (II), and Zeolite or activated carbon is used as a support. However, the production conditions are water/methanol, water/acetone, and from the industrial point of view, it is not suitable for obtaining a purified hydrogen peroxide final product, and the reaction pressure is also as high as 1 Mpa or more.

Patent Document 9 proposes a catalyst for obtaining hydrogen peroxide comprising at least one metal selected from Groups 7 to 11 of the periodic table and supporting an acidic group bonded by the surface of the metals The functionalized SiO ₂ has a reaction pressure of 9.6 MPa, is very high, and is in a methanol-based reaction, and a purification step is required in order to obtain a final product.

Patent Document 10 proposes a method for producing hydrogen peroxide, which comprises the step of reacting hydrogen with oxygen in a solvent in the presence of a cationic polymer containing a noble metal and a halogen-containing anion, but the method is also carried out in a methanol medium.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 56-47121

[Patent Document 2] Japanese Patent Publication No. 55-18646

[Patent Document 3] Japanese Special Fair No. 1-341001

[Patent Document 4] Japanese Patent Laid-Open Publication No. SHO 63-156005

[Patent Document 5] Japanese Patent Laid-Open No. Hei 8-2904

[Patent Document 6] Japanese Patent Laid-Open No. Hei 9-301705

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2008-212872

[Patent Document 8] Japanese Special Table 2009-500171

[Patent Document 9] Japanese Patent Laid-Open Publication No. 2008-296213

[Patent Document 10] Japanese Patent Laid-Open Publication No. 2009-542565

The direct production method of hydrogen peroxide is important in terms of the production efficiency which is influenced by factors such as the selectivity of the synthesis reaction and the rate of formation. In this regard, according to the above conventional method, a certain degree of hydrogen peroxide can be produced. But the above conventional methods are not The reaction is carried out in a state in which the selectivity, the production rate, the yield, and the like are comprehensively satisfied, and in order to improve the reaction performance, a high reaction pressure is required, and some water/methanol and water/acetone reaction solutions are used, and the current state is industrial production. Restricted, or not at a level that is economically satisfactory.

The present invention has been developed based on the above background, and aims to provide a direct and stable production of peroxidation from hydrogen and oxygen by using a low pressure of about 1 atm in an aqueous medium without using an organic solvent. Hydrogen method.

In order to solve the above problems, the inventors of the present invention have intensively studied the relationship between the crystal structure of titanium oxide (titania) and the rate of formation of hydrogen peroxide and the selectivity, and found that the brookite-type titanium oxide is used as a support. The carrier is supported by a catalyst containing at least one active metal selected from the group consisting of platinum, palladium, silver, and gold. When hydrogen and oxygen are reacted to produce hydrogen peroxide, the balance can be improved with good balance. The reaction rate, selectivity and yield are the completion of the present invention.

That is, the above problems can be solved by the following invention.

<1> A direct method for producing hydrogen peroxide, comprising the steps of: supporting a brookite-type titanium oxide carrying at least one active metal selected from the group consisting of platinum, palladium, silver, and gold; In the presence of a catalyst, hydrogen is reacted with oxygen.

<2> The direct production method of hydrogen peroxide according to <1>, wherein the weight of the active metal is 0.01 to 10% by weight based on the brookite-type titanium oxide.

<3> The direct production method of hydrogen peroxide according to <1> or <2>, wherein the catalyst system is previously subjected to hydrogen reduction at a temperature of 400 ° C or higher.

<4> The direct production method of hydrogen peroxide according to any one of <1> to <3> wherein the catalyst is reduced by hydrazine.

The direct production method of hydrogen peroxide according to any one of <1> to <4> wherein the above-mentioned catalyst is further loaded and selected from the group consisting of ruthenium, osmium, iridium and osmium. One or more.

<6> The direct production method of hydrogen peroxide according to any one of <1> to <5> wherein the active metal is palladium and/or gold.

<7> The direct production method of hydrogen peroxide according to <6>, wherein the active metal is palladium and gold, and the molar ratio of palladium/gold is from 0.1 to 10.

The direct production method of hydrogen peroxide according to any one of <1> to <7> wherein the brookite-type titanium oxide has a specific surface area of at least 50 m ² /g.

<9> The direct production method of hydrogen peroxide according to any one of <1> to <8>, wherein hydrogen peroxide is produced in the absence of an organic solvent.

<10> The direct production method of hydrogen peroxide according to any one of <1> to <9> wherein the reaction is carried out by adding a mineral acid selected from hydrogen halide or sulfuric acid and reacting.

<11> The direct production method of hydrogen peroxide according to <10>, wherein the amount of the inorganic acid added is 0.01 to 10% by weight based on the reaction solution.

According to the production method of the present invention, brookite-type titanium oxide can be used as a catalyst carrier without using an anatase-type or rutile-type titanium oxide known as a carrier of a conventional catalyst. Good balance improves the reaction rate, selectivity and yield of hydrogen peroxide, and can obtain a high concentration of aqueous hydrogen peroxide solution in a short reaction time. Further, since the present invention does not require the use of an organic solvent, there is an advantage that a finishing step is not required in order to obtain a final product.

[Formation of the Invention]

The invention is described in detail below.

In the present invention, the catalyst carrier can be used as long as it is a brookite-type titanium oxide, and is not particularly limited. The brookite-type titanium oxide, for example, has a crystal structure having a density of 4.13 g/cm ³ , a lattice constant: a = 5.45 Å, b = 9.18 Å, and c = 5.15 Å.

These brookite-type titanium oxides can also be identified by X-ray diffraction.

Further, the specific surface area of the catalyst carrier is important. In the present invention, the brookite-type titanium oxide which is a catalyst carrier is preferably a large specific surface area, more preferably 10 m ² /g or more, and particularly preferably 50 m. ² / g or more. Further, the upper limit of specific surface area of 150m ² / g or less preferably, 100m ² / g or less more preferably.

The catalyst used in the present invention is one in which at least one active metal selected from the group consisting of platinum, palladium, silver, and gold is carried on the brookite-type titanium oxide supported on the support. The above active metal, specifically, platinum, palladium, silver or gold may be used singly or in the form of a mixture or an alloy. In the present invention, one or more selected from the group consisting of ruthenium, osmium, iridium and osmium may be used in the form of a mixture or an alloy, insofar as the effect of the present invention is not impaired.

In the present invention, it is preferred to use palladium and/or gold as the above active metal. Palladium/gold molar ratio. Depending on the state of dispersion of the active metal supported on the brookite-type titanium oxide as the support, it is preferably 0.1 to 10, more preferably 1 to 5.

In the method of supporting the above-mentioned active metal on the brookite-type titanium oxide as a support, it is preferred to use an impregnation method or an ion exchange method. For the impregnation method, an evaporation dry solid method, an equilibrium adsorption method, a pore filling method, or the like can be applied. The support amount of the active metal to the support is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight based on the weight of the support. Further, in the direct production method of hydrogen peroxide of the present invention, the amount of the catalyst used is preferably from 1 to 100 g/l, more preferably from 5 to 40 g/l, based on the reaction liquid.

Further, the method of supporting the active metal on the brookite-type titanium oxide may be preferably carried out by suspending the titanium oxide in an aqueous solution in which the metal salt of the active metal is dissolved, and then reducing and carrying it with a reducing agent. . As the above reducing agent, oxalic acid, hydrazine or formalin can be used, and among them, a hydrazine is preferably used. Further, when it is used as a reaction catalyst, it is preferred to carry out hydrogen reduction at a temperature of 200 ° C or higher, more preferably 300 ° C, and particularly preferably 400 ° C or higher.

Further, in the method of the present invention, it is preferred to add a mineral acid to the reaction system to make the reaction better. Thereby, the selectivity of the hydrogen peroxide synthesis reaction can be increased, and the production efficiency can be ensured. The amount of the inorganic acid to be added is preferably 0.01 to 10% by weight based on the reaction solution. Further, it is preferred to use a hydrogen halide or sulfuric acid as the inorganic acid, and it is preferred to add one or both of them.

The reaction temperature in the synthesis reaction is preferably from 0 to 100 ° C, particularly preferably from 5 to 50 ° C. The pressure of the reaction is not particularly limited, and is preferably from atmospheric pressure to 10 MPa, and particularly preferably from atmospheric pressure to 2 MPa. The reaction time is usually from 0.1 to 100 hours, preferably from 0.5 to 10 hours. The reaction can be carried out batchwise or continuously. Further, it is preferable that the flow rate of hydrogen gas and oxygen gas to be a raw material is such that the explosion range is avoided and the ratio of oxygen to hydrogen is excessive.

In the present invention, the reaction rate of hydrogen is preferably 30% or more, more preferably 40% or more. Further, in the present invention, the selectivity of hydrogen peroxide is preferably 40% or more, more preferably 60% or more. Further, in the present invention, the yield of hydrogen peroxide is preferably 25% or more.

[Examples]

Hereinafter, the present invention will be more specifically described based on examples and comparative examples, but the present invention is not limited to the following examples.

(Example 1)

10 g of a high surface area brookite-type titanium oxide (specific surface area: 74 m ² /g), HAuCl ₄ 0.05 g, and PdCl ₂ 0.12 g were suspended in 300 ml of water and heated to 60 ° C. After adding NaOH (2.5 × 10 ^-4 mol/ml) until the pH became 10, a 3% aqueous hydrazine solution was added dropwise. When the color does not change, it is judged that the reduction is completed, and then heated while stirring with a magnetic stirrer to remove moisture to become semi-liquid. Further, after removing the magnetic stirrer, it was dried overnight at 85 ° C in a dryer. The dried sample was granulated to 0.5 to 1.8 mm, and subjected to reduction treatment in a H ₂ gas stream at 450 ° C and 40 ml/min for 4 hours to obtain a black granular catalyst. Check the X-ray diffraction of the obtained catalyst. The result is shown in Figure 1.

1.5 g of a brookite-type titanium oxide catalyst supported by the above-mentioned Au/Pd, 0.368 g of NaCl, and 2.8 g of sulfuric acid were placed in a 230 ml autoclave equipped with a stirring device and a gas injection tube. The diluted water was diluted and added to make the whole amount 75 ml. The pressure cooker was adjusted to a state of 10 ° C, and the pressure was adjusted to 0.1 M while blowing a gas at 50 ml/min (hydrogen: 2.5%, oxygen: 19.5%, nitrogen: 30%, argon: 48%). The mixture was reacted for 2 hours at a stirring speed of 800 rpm.

(1) The rate of formation of hydrogen peroxide is determined in the following manner.

Hydrogen peroxide generation rate = (molar concentration of hydrogen peroxide generated) ÷ (reaction time)

Further, the molar concentration of the generated hydrogen peroxide is a titanyl sulfate as a coloring agent for hydrogen peroxide, and an ultraviolet-visible spectrophotometer (trade name: V-550, Japan Spectrophotometer) is used. Determination.

(2) The reaction rate of hydrogen is determined in the following manner.

Hydrogen reaction rate = (amount of hydrogen consumed) ÷ (total amount of hydrogen blown)

In addition, the amount of hydrogen gas consumed was measured by gas chromatography (trade name: GC-8A, manufactured by Shimadzu Corporation).

(3) The selectivity of hydrogen peroxide is calculated in turn.

The selectivity (%) of hydrogen peroxide = [(the amount of hydrogen peroxide generated by the reaction) ÷ (the theoretical amount of hydrogen peroxide calculated from the amount of hydrogen consumed)] × 100

Further, the amount of hydrogen peroxide generated was measured using a titanium oxysulfate as a coloring agent of hydrogen peroxide and using an ultraviolet-visible spectrophotometer (trade name: V-550, manufactured by JASCO Corporation).

(4) The yield of hydrogen peroxide was determined in the following manner.

Yield of hydrogen peroxide = (reaction rate of hydrogen) × (selectivity of hydrogen peroxide)

These results are shown in Table 1.

(Example 2) (evaporation dry solid method)

10 g of a high surface area brookite-type titanium oxide (specific surface area: 74 m ² /g), 0.05 g of HAuCl ₄ and 0.12 g of PdCl _{2 were} suspended in 100 ml of water. The mixture was heated while stirring with a magnetic stirrer to remove moisture until it became semi-liquid. Furthermore, after removing the magnetic stirrer, it was dried overnight at 60 °C. The dried sample was pulverized, granulated to 0.5 to 1.18 mm, and subjected to reduction treatment in an H ₂ gas stream at 450 ° C and 40 ml/min for 4 hours to obtain a black granular catalyst. The X-ray diffraction of the obtained catalyst was examined. The result is shown in Figure 2.

Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The results obtained are shown in Table 1.

(Example 3)

10 g of a high surface area brookite-type titanium oxide (specific surface area: 74 m ² /g), 0.086 g of HAuCl ₄ and 0.203 g of PdCl ₂ were suspended in 300 ml of water and heated to 60 ° C. After adding NaOH (2.5 × 10 ^-4 mol/ml) to bring the pH to 10, a 3% aqueous hydrazine solution was added dropwise. When the color is no longer changed, it is judged that the reduction is completed, and while stirring with a magnetic stirrer, the water is heated and removed until it becomes semi-liquid. Further, after removing the magnetic stirrer, it was dried overnight at 85 ° C in a dryer. The dried sample was granulated to 0.5 to 1.8 mm to obtain a particulate catalyst.

Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The results obtained are shown in Table 1.

(Example 4)

10 g of a high surface area brookite-type titanium oxide (specific surface area: 74 m ² /g) and 0.203 g of PdCl ₂ were suspended in 300 ml of water and heated to 60 ° C. NaOH (2.5 × 10 ^-4 mol/ml) was added until the pH became 10, and a 3% aqueous hydrazine solution was added dropwise. When the color is no longer changed, it is judged that the reduction is completed, and the magnetic stirring is continued while stirring with a magnetic stirrer to remove the water until it becomes semi-liquid. Further, after removing the magnetic stir bar, it was dried overnight at 85 ° C in a dryer. The dried sample was granulated to 0.5 to 1.8 mm to obtain a particulate catalyst.

Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The results obtained are shown in Table 1.

(Example 5)

10 g of high surface area brookite-type titanium oxide (specific surface area: 74 m ² /g), PdCl ₂ 0.203 g, and Pt(NH ₃ ) ₄ Cl ₂ ‧H ₂ O 0.22 g were suspended in 300 ml of water and heated to 300 °C. 60 ° C. After adding NaOH (2.5 × 10 ^-4 mol/ml) to bring the pH to 10, a 3% aqueous hydrazine solution was added dropwise. When the color is no longer changed, it is judged that the reduction is completed, and the magnetic stirring is continued while stirring with a magnetic stirrer to remove the water until it becomes semi-liquid. Further, after removing the magnetic stir bar, it was dried overnight at 85 ° C in a dryer. The dried sample was granulated to 0.5 to 1.8 mm to obtain a particulate catalyst.

Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The results obtained are shown in Table 1.

(Comparative Example 1)

10 g of ruthenium-based rutile-type titanium oxide (STR-100N, surface area: 38 m ² /g), HAuCl ₄ 0.05 g, and PdCl ₂ 0.12 g, which were previously calcined in air at 500 ° C for 2 hours, were suspended in 100 ml of water. The mixture was heated with a magnetic stirrer to remove water until it became semi-liquid. Further, after removing the magnetic stir bar, it was dried overnight at 60 °C. The dried sample was pulverized, granulated to 0.5 to 1.18 mm, and subjected to reduction treatment in a H ₂ gas stream at 450 ° C and 40 ml/min for 4 hours to obtain a black granular catalyst.

Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The results obtained are shown in Table 1.

(Comparative Example 2)

10 g of ruthenium-based titanium oxide (STR-100N, surface area: 38 m ² /g), 0.05 g of HAuCl ₄ and 0.12 g of PdCl _{2 were} suspended in 300 ml of water and heated to 60 °C. NaOH (2.5 × 10 ^-4 mol/ml) was added until the pH became 10, and a 3% aqueous hydrazine solution was added dropwise. When the color is no longer changed, it is judged that the reduction is completed, and the water is heated and removed while stirring with the magnetic stirrer until it becomes semi-liquid. Further, after removing the magnetic stir bar, it was dried overnight at 85 ° C in a dryer. The dried sample was granulated to 0.5 to 1.8 mm, and subjected to reduction treatment in a H ₂ gas stream at 450 ° C and 40 ml/min for 4 hours to obtain a black granular catalyst.

Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The results obtained are shown in Table 1.

(Comparative Example 3)

10 g of anatase type titanium oxide (020-78675; surface area 5.8 m ² /g) of KISHIDA Chemical, 0.05 g of HAuCl ₄ and 0.12 g of PdCl _{2 were} suspended in 100 ml of water. The water was heated and removed while stirring with a magnetic stirrer until it became semi-liquid. Further, after removing the magnetic stir bar, it was dried overnight at 60 °C. The dried sample was pulverized, granulated to 0.5 to 1.18 mm, and subjected to reduction treatment in a H ₂ gas stream at 450 ° C and 40 ml/min for 4 hours to obtain a black granular catalyst.

Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The results obtained are shown in Table 1.

From the results shown in Table 1, it is known that the use of brookite according to Examples 1 to 5 is utilized. The method for producing hydrogen peroxide of the present invention in which a titanium oxide is supported by a specific active metal catalyst is produced by using hydrogen peroxide which is a catalyst for carrying a metal of rutile-type titanium oxide and anatase-type titanium oxide. The method has excellent balance between the formation rate of hydrogen peroxide, the selectivity and the yield, and particularly has a high selectivity, and can be considered to have industrial value. Especially in the case of a gas circulation type reaction system, a high selectivity is economically very advantageous.

Figure 1 shows an X-ray diffraction pattern of the catalyst obtained in Example 1.

2 shows an X-ray diffraction pattern of the catalyst obtained in Example 2.

Claims (11)

A direct method for producing hydrogen peroxide, comprising the steps of: supporting a catalyzed titanium oxide supported by at least one active metal selected from the group consisting of platinum, palladium, silver, and gold; Next, react hydrogen with oxygen. The direct production method of hydrogen peroxide according to the first aspect of the invention, wherein the weight of the active metal is 0.01 to 10% by weight based on the brookite-type titanium oxide. The direct production method of hydrogen peroxide according to claim 1 or 2, wherein the catalyst is previously subjected to hydrogen reduction at a temperature of 400 ° C or higher. The direct production method of hydrogen peroxide according to any one of claims 1 to 3, wherein the catalyst is reduced by a hydrazine. The direct manufacturing method of hydrogen peroxide according to any one of claims 1 to 4, wherein the catalyst is further loaded with one selected from the group consisting of ruthenium, osmium, iridium and osmium. the above. The direct production method of hydrogen peroxide according to any one of claims 1 to 5, wherein the active metal is palladium and/or gold. The direct production method of hydrogen peroxide according to claim 6, wherein the active metal is palladium and gold, and the palladium/gold molar ratio is 0.1 to 10. The direct production method of hydrogen peroxide according to any one of claims 1 to 7, wherein the brookite-type titanium oxide has a specific surface area of at least 50 m ² /g. The direct production method of hydrogen peroxide according to any one of claims 1 to 8, which is to produce hydrogen peroxide in the absence of an organic solvent. The direct production method of hydrogen peroxide according to any one of claims 1 to 9, wherein the reaction is carried out by adding a mineral acid selected from hydrogen halide or sulfuric acid and reacting. The direct production method of hydrogen peroxide according to claim 10, wherein the inorganic acid is added in an amount of 0.01 to 10% by weight based on the reaction solution.