KR20180025716A - Catalyst composition for decompositioning high concentrated hydrogen peroxide and method for producing the same - Google Patents

Abstract

The present invention relates to a method for manufacturing a metal catalytic composition for decomposing high-concentrated hydrogen peroxide. The present invention provides a method for manufacturing a metal catalytic composition for decomposing high-concentrated hydrogen peroxide which comprises the following steps: a step for manufacturing a mixture by dissolving a manganese compound, an aluminum compound and a lanthanum precursor in a certain solvent; a step for precipitating catalysts in a powder form in the mixture, and drying the precipitated catalysts in the powder form; a step for calcining the catalysts in the powder form at a temperature of 400-800°C; a step for mixing a binder solution and methylcellulose with the catalysts in the powder form, and manufacturing a mold body by forming in a predetermined shape; and a step for calcining the mold body at a temperature of 400-800°C. According to the present invention, the catalyst activity and lifetime can be enhanced over conventional catalysts in hydrogen peroxide decomposition.

Description

TECHNICAL FIELD The present invention relates to a catalyst composition for high-concentration hydrogen peroxide decomposition and a method for producing the catalyst composition,

The present invention relates to a method for preparing a metal catalyst composition for high-concentration hydrogen peroxide decomposition.

Hydrogen peroxide is decomposed into water vapor and oxygen by the chemical decomposition reaction when it comes into contact with the catalyst. Since it can generate heat and pressure to generate propulsion, it is used in artificial thruster and propulsion machinery. Zero is in the spotlight.

Hydrogen peroxide is a propellant itself, which is less toxic and easy to handle and requires no special safety measures required for handling other toxic propellants, so it can be handled at low cost. Usually propellants are high-peroxide (HTP), high-strength peroxide or rocket grade peroxide.

When the high concentration hydrogen peroxide decomposition method is used for a series of intermittent decomposition in a spacecraft or the like, it is essential that not only an effective and continuous catalytic activity should be exhibited but also an excellent thermo-mechanical property and a long service life.

In the prior art, catalyst materials most frequently used for decomposing hydrogen peroxide at high concentration include manganese (Mn), silver (Ag), platinum (Pt), and the like as a support such as a screen, a pellet or a honeycomb, ), Palladium (Pd), ruthenium (Ru), iridium (Ir) and the like, and many technologies related to a catalyst for decomposing high concentration hydrogen peroxide using such a catalyst have been known. However, Table 1 shows the results.

According to Table 1, US Pat. No. 2,721,788 discloses a method of decomposing high concentration hydrogen peroxide using a catalyst coated with manganese on a ceramic pellet or a wire screen. U.S. Patent No. 3,560,407 describes a method of decomposing high concentration hydrogen peroxide using a screen-type catalyst in which an alloy of silver and palladium is etched and coated with a samarium oxide. U.S. Patent No. 5,711,146 discloses a method for decomposing high-concentration hydrogen peroxide using a catalyst loaded with ruthenium-platinum, ruthenium-iridium, ruthenium-platinum-iridium on an alumina pellet support or a nickel wire screen. U.S. Patent No. H1948 H describes a method for decomposing high-concentration hydrogen peroxide using a catalyst bed in which manganese and an alkali metal (sodium or potassium) are coated on a honeycomb support made of ceramics such as alumina, silica, and aluminosilicate .

As the published paper, iridium-supported catalysts for gamma-alumina support were used as catalysts for decomposing hydrogen peroxide at high concentration, but catalysts were inactivated easily (Non-Patent Document 1). The results of using La01-xKxMnO3 type perovskite as a catalyst for decomposing hydrogen peroxide at high concentration have been reported in the literature, but the disadvantage is that the decomposition efficiency is not high (Non-Patent Document 2). It has been reported that using a catalyst containing titania as a support and carrying manganese oxide has a high concentration of hydrogen peroxide decomposition activity, but there is a problem that the deactivation proceeds rapidly with the lapse of time (Non-Patent Document 3). A method of decomposing high concentration hydrogen peroxide using a catalyst containing manganese, platinum, silver or ruthenium using pellet-shaped alumina or the like as a support is known, but a catalyst containing only manganese is inactivated rapidly, and a catalyst using a noble metal There is a drawback that the price is expensive.

As to the type of catalyst, various types of catalysts such as pellet type catalyst, screen catalyst and monolith type catalyst are generally used for reducing the activation energy in the hydrogen peroxide decomposition reaction. The catalyst forms for hydrogen peroxide decomposition are shown in Table 2 below.

In the case of the pellet type catalyst, the contact between the catalysts is small in the form of an angle or a dot, and the heat transfer between the catalysts is caused by the convection rather than the conduction. In the case of the screen catalyst, the increase in the amount of decomposition treatment increases the erosion of the screen, thereby increasing the loss and shortening the catalyst life. In the case of the monolith type catalyst, problems such as packing and catalyst abrasion have.

US 2721788 B1 US 2560407 B1 US 5711146 B1 US, H1948, H

 Appl Catala 210, 55, 2001  Appl Catala 215, 245, 2001  J Propul Power 20 (6), 1069, 2001  AIAA Propulsion Conference, 2007  AIDAA Congress, 2009  Catal comm. 12, 286, 2005  AIAA Conference, 2005  Korean Society of Propulsion Engineers, 9 (4), 1, 2005  Korea Society of Mechanical Engineers, 11 (1), 18, 2007  Korean Society of Propulsion Engineers, 12 (3), 24, 2008  Aerospace Sci. Technol. 13 (1), 12, 2009

 It is an object of the present invention to provide a catalyst composition having improved activity and service life during decomposition of high-concentration hydrogen peroxide and a method of producing a catalyst composition in the form of a metal foam.

In order to accomplish the above object, the present invention provides a process for producing a mixture comprising the steps of preparing a mixture by dissolving a manganese compound, an aluminum compound and a rhodium precursor in a solvent, precipitating a powdery catalyst from the mixture, drying the precipitated powdery catalyst Calcining the powdery catalyst at a temperature of 400 to 800 ° C, mixing the binder solution and methylcellulose with the powdery catalyst, molding the mixture into a predetermined shape to produce a molded article, To 800 < 0 > C.

In one embodiment, in the step of preparing the molded body, the binder solution is composed of a mixture of a pseudoboehmite solution and an aqueous nitric acid solution. The mass ratio of the pseudo boehmite to the mass of the catalyst in powder form May be 0.05 to 0.2.

In one embodiment, in the step of preparing the molded body, the mass ratio of the methylcellulose to the mass of the catalyst in powder form may be 0.01 to 0.1.

The present invention also provides a metal catalyst composition. Wherein the metal catalyst composition comprises manganese oxide, lanthanum oxide, and aluminum oxide, wherein the mass ratio of manganese (Mn / Al) to the mass of aluminum contained in the composition is 0.5 to 4.5, and manganese , The mass ratio of lanthanum to the total mass of lanthanum and aluminum (La / (Mn + La + Al)) is 0.05 to 0.30.

The present invention also provides a method for preparing a precursor aqueous solution, comprising the steps of: preparing a precursor aqueous solution by mixing at least one of a K-Mn precursor, a Mn precursor, Pb, Ni, Cu, Ce Bi, A step of coating the precursor aqueous solution, drying the metal foam coated with the precursor aqueous solution at a temperature of 100 to 120 DEG C for 10 to 14 hours, and calcining the metal foam, A method for preparing a composition is provided.

In one embodiment, the step of preparing the precursor aqueous solution further comprises mixing at least one of Al ₂ O ₃ and Fe ₂ O ₃ , wherein the precursor dissolved in the precursor aqueous solution is selected from the group consisting of acetate, And chloride.

In one embodiment, the metal foam may be an Ni-Fe-Cr or Ni-Cr-Al alloy.

In one embodiment, the firing may be performed at a temperature of 600 to 900 ° C. for 3 to 5 hours while the metal foam is in contact with at least one of nitrogen, air, and oxygen.

According to the present invention, catalyst activity and lifetime can be improved over conventional catalysts in hydrogen peroxide decomposition.

1 is a conceptual diagram showing a method for testing the performance of a catalyst composition prepared according to an embodiment of the present invention.
FIG. 2 is a graph showing the maximum liquid-phase temperature (Tmax) according to the number of injections when decomposing high-concentration hydrogen peroxide using the catalyst compositions prepared according to Examples 1 to 3 and Comparative Examples.
FIG. 3 is a graph showing the time at which the liquid phase maximum temperature (Tmax) is reached when the high concentration hydrogen peroxide is decomposed using the catalyst compositions prepared according to Examples 1 to 3 and Comparative Examples.
4 is a flowchart illustrating a method of manufacturing a metal foam catalyst according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings, wherein like reference numerals are used to designate identical or similar elements, and redundant description thereof will be omitted. In the following description of the embodiments of the present invention, a detailed description of related arts will be omitted when it is determined that the gist of the embodiments disclosed herein may be obscured. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed. , ≪ / RTI > equivalents, and alternatives.

The present invention provides a process for preparing a manganese-aluminum-lanthanum catalyst composition and a catalyst composition in the form of a metal foam, respectively.

First, a method of preparing the manganese-aluminum-lanthanum catalyst composition according to the present invention will be described in detail.

First, a step of preparing a mixture by dissolving a manganese compound, an aluminum compound, and a rhodium precursor in a predetermined solvent is performed.

Here, the predetermined solvent may be distilled water.

The lanthanum metal has the effect of increasing the surface area of manganese and preventing the surface area of manganese from decreasing due to sintering of the manganese particles by the heat of reaction as the high concentration hydrogen peroxide decomposition reaction occurs repeatedly. In the catalyst of the present invention, lanthanum is a lanthanum oxide, and manganese 4 plays a role of maintaining cations and is effective for hydrogen peroxide decomposition reaction. These effects are complexly expressed, and are highly effective at high concentration of hydrogen peroxide decomposition.

The manganese compound may be any one of manganese sulfate, manganese nitrate, manganese chloride, manganese bromide, manganese carbonate, manganese acetylacetonate, manganese acetic acid, manganese hydroxide, manganese oxide and manganese dioxide, preferably manganese nitrate.

The aluminum compound may be any one of aluminum oxide, aluminum nitrate, aluminum sulfate, aluminum hydroxide, aluminum ethylate, aluminum phosphate and aluminum chloride, preferably aluminum nitrate.

The lanthanum compound may be lanthanum nitrate or lanthanum chloride, preferably lanthanum nitrate.

Next, a step of precipitating a catalyst in the form of a powder from the mixture and drying the catalyst in the form of a precipitated powder is carried out.

After the mixture is prepared, the pH is adjusted to 7 to 7.5 while maintaining the temperature of the mixture at room temperature to 100 ° C, preferably 50 to 80 ° C, and aged sufficiently until a precipitate is formed.

At this time, a basic precipitant may be further used as a precipitant for the precipitation process. The precipitant may be selected from the group consisting of sodium hydroxide, sodium carbonate, potassium hydroxide, ammonium hydroxide, ammonia gas, ammonium hydrogen carbonate, ammonium carbonate, sodium oxalate, potassium oxalate and ammonium oxalate It can be either.

Next, the precipitated powdery catalyst is washed with distilled water and dried.

Next, the step of calcining the powdery catalyst at a temperature of 400 to 800 캜 is carried out.

The catalyst obtained by the above-mentioned method is used in the form of pellets or granules.

Specifically, after the catalyst in powder form is calcined, the binder solution and methyl cellulose are mixed with the catalyst in the form of powder, and the step of molding into a predetermined form is performed.

Here, the binder solution is prepared by mixing a pseudoboehmite with a predetermined solvent and then adding an aqueous nitric acid solution.

The powdery catalyst, the binder solution and the mixture of methylcellulose may be formed into pellets by a twin screw extruder.

Thereafter, the molded body is dried and then fired at a temperature of 400 to 800 ° C.

The manganese-lanthanum-aluminum-based catalyst composition prepared by the above-mentioned method is characterized in that the composition is composed of manganese oxide, lanthanum oxide and aluminum oxide, and the mass ratio of manganese (Mn / Al) To 4.5. Preferably, Mn / Al can be 1.0 to 3.3. When Mn / Al is less than 0.5, it is difficult to maintain the activity of the catalyst. When the Mn / Al is more than 4.5, the compressive strength of the formed catalyst decreases and the lifetime of the catalyst decreases.

Meanwhile, the mass ratio (La / (Mn + La + Al)) of the lanthanum to the total mass of manganese, lanthanum and aluminum contained in the composition may be 0.05 to 0.30. Preferably, La / (Mn + La + Al) may be 0.1 to 0.2.

Hereinafter, a method for producing a catalyst composition in the form of a metal foam will be described.

At least one of the K-Mn precursor, Mn precursor, Pb, Ni, Cu, Ce Bi, Pt and Ag precursors is mixed with a solvent to prepare a precursor aqueous solution.

Here, at least one of Al ₂ O ₃ and Fe ₂ O ₃ may be further mixed with distilled water in the precursor aqueous solution.

On the other hand, at least one of an organic binder such as carboxymethylcellulose sodium salt and an inorganic binder such as alumina sol may be added to the precursor aqueous solution.

The precursor dissolved in the aqueous solution of the precursor may be any one of acetate, sulfate, nitrate and chloride.

Next, a step of coating the precursor aqueous solution on the surface of a predetermined type of metal foam is performed.

The metal foam may be an Ni-Fe-Cr or Ni-Cr-Al alloy.

On the other hand, the object to be coated with the precursor aqueous solution may be a mold composed of a plurality of cells as well as a metal foam made of a metal. Such a cell can have various shapes, and the number of cells can be variously adjusted. For example, the cell may have a size of about 800 μm or more and 3000 μm or less.

Next, the step of drying the metal foam coated with the precursor aqueous solution is performed.

Here, the drying temperature may be 100 to 120 ° C and the drying time may be 11 to 13 hours.

Finally, the step of calcining the metal foams proceeds.

Here, the firing temperature may be 600 to 900 占 폚, and the firing time may be fired for 3 to 5 hours while the metal foam is in contact with at least one of nitrogen, air, and oxygen.

Hereinafter, a method for analyzing the high concentration hydrogen peroxide decomposition activity and the lifetime of the catalyst composition according to the present invention will be described.

As shown in Fig. 1, a volume of 100 ml reactor made of Inconel 600 is filled with a certain amount of catalyst in the form of pellets or granules, and a certain amount of high-concentration hydrogen peroxide is injected into the reactor.

Simultaneously with the introduction of high concentration hydrogen peroxide, the temperature and pressure of the liquid and gas phase inside the reactor and the flow rate of the produced gas are measured 100 times per second. The activity of the high concentration hydrogen peroxide decomposition catalyst was evaluated by analyzing the maximum liquid temperature (Tmax) and the maximum liquid temperature (tmax). The higher the maximum liquid temperature (Tmax) and the maximum liquid temperature ) Is shorter, the high concentration of hydrogen peroxide decomposition activity is good.

After the high concentration hydrogen peroxide decomposition test is completed and the temperature and pressure inside the reactor are restored to the initial state, the above-mentioned high concentration hydrogen peroxide decomposition experiment is repeatedly performed while keeping the catalyst in the reactor as it is. The above-described high-concentration hydrogen peroxide decomposition experiment is repeated several times or more to evaluate the lifetime of the catalyst by analyzing whether the maximum liquid temperature (Tmax) and the maximum liquid temperature (tmax) are maintained.

As a result of decomposing the high concentration hydrogen peroxide using the catalyst of the present invention, the activity of the catalyst was maintained even after repeating the high concentration hydrogen peroxide decomposition experiment 35 times or more.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the scope and contents of the present invention are not construed to be limited or limited by the following Examples and Experimental Examples.

Example 1. Preparation of metal catalyst compositions based on manganese-aluminum-lanthanum

52.8 g of manganese nitrate (hexahydrate), 72.0 g of aluminum nitrate (9 hydrate) and 23.8 g of lanthanum nitrate (hexahydrate) were dissolved in 300 ml of distilled water to prepare a metal precursor solution and then heated to 70 캜.

68 mL of ammonium hydroxide was mixed with distilled water to prepare 1 L of precipitant solution and then heated to 70 캜.

200 ml of distilled water was placed in a round flask and the impeller was placed. The impeller was heated to 70 ° C. and the solution of the metal precursor was slowly added thereto while maintaining the temperature of the solution at 70 ° C. and sufficiently stirred with an impeller. The positive precipitant solution was added and stirred for 1 hour.

The precipitate was filtered and washed three more times with distilled water. The precipitate was dried and calcined at 500 DEG C for 4 hours or more in an air atmosphere.

27.8 g of pseudoboehmite was mixed with 56.8 g of distilled water and stirred for 30 minutes to prepare a pseudobohemite solution. 1.17 g of nitric acid (60%) was mixed with 14.2 g of distilled water to prepare a nitric acid aqueous solution. The pseudoboehmite solution and nitric acid aqueous solution were mixed and sufficiently stirred to prepare a binder solution. 21.4 g of the inorganic binder solution and 2.5 g of methylcellulose were mixed with 50 g of the powdery catalyst, and 50 g of distilled water was mixed and kneaded. A pellet type catalyst having a diameter of 2 mm was prepared by using this twin screw extruder. The pellet-shaped catalyst was dried and then calcined at 500 ° C.

The pellet type catalyst was pulverized to prepare a granule type catalyst having a size of 1.0 to 1.2 mm. The composition of the resulting catalyst was in the form of an oxide, and the composition ratio of each component was 55.8 wt% of manganese, 26.3 wt% of aluminum, and 17.9 wt% of lanthanum in terms of oxides.

A volume of 100 ml reactor manufactured by Inconel 600 was filled with 2 g of granular catalyst having a size of 1.0 to 1.2 mm, and a predetermined amount of hydrogen peroxide (8 mL) was pulsed at a 90% concentration. Simultaneously with the introduction of high concentration hydrogen peroxide, the temperature of the liquid phase inside the reactor was measured 100 times per second. As a result, 2.3 seconds passed after the start of the reaction, and the maximum temperature reached 153.1 ^° C.

After the above-mentioned high-concentration hydrogen peroxide decomposition experiment was completed and the temperature and pressure inside the reactor were recovered to the initial state, the above-mentioned high-concentration hydrogen peroxide decomposition experiment was repeatedly performed while keeping the catalyst in the reactor. After the high concentration hydrogen peroxide decomposition experiment was repeated 15 times, the temperature of the liquid phase in the reactor was measured. As a result, 2.6 seconds elapsed after the start of the reaction, the maximum temperature reached 164.0 ^° C. After the high-concentration hydrogen peroxide decomposition experiment was repeated 35 times, the temperature of the liquid phase in the reactor was measured. As a result, 4.3 seconds elapsed after the start of the reaction, the maximum temperature reached 165.6 ^° C.

Example 2. Preparation of manganese-aluminum-lanthanum based metal catalyst compositions

52.8 g of manganese nitrate (hexahydrate), 72.0 g of aluminum nitrate (9 hydrate) and 23.8 g of lanthanum nitrate (hexahydrate) were dissolved in 300 ml of distilled water to prepare a metal precursor solution and then heated to 70 캜.

68 mL of ammonium hydroxide was mixed with distilled water to prepare 1 L of precipitant solution and then heated to 70 캜. 200 ml of distilled water was placed in a round flask, the impeller was placed, and then heated to 70 ° C. While the metal precursor solution was gradually added thereto, the temperature of the solution was maintained at 70 DEG C, and a sufficient amount of the precipitant solution was added thereto so that the pH was 7 to 7.5 while stirring thoroughly with the impeller, followed by stirring for 1 hour. The precipitate was filtered and washed three more times with distilled water. The precipitate was dried and then calcined at 500 DEG C for 4 hours or more in an air atmosphere.

27.8 g of pseudoboehmite was mixed with 56.8 g of distilled water and stirred for 30 minutes to prepare a pseudobohemite solution. 1.17 g of nitric acid (60%) was mixed with 14.2 g of distilled water to prepare a nitric acid aqueous solution. Pseudo boehmite solution and nitric acid aqueous solution were mixed and sufficiently stirred to prepare an inorganic binder solution. 10.3 g of the inorganic binder solution and 2.5 g of methylcellulose were mixed with 50 g of the powdery catalyst, and 50 g of distilled water was mixed and kneaded. A pellet type catalyst having a diameter of 2 mm was prepared by using this twin screw extruder. The pellet-shaped catalyst was dried and then calcined at 500 ° C. The pellet type catalyst was pulverized to prepare a granule type catalyst having a size of 1.0 to 1.2 mm. The composition of the resulting catalyst was obtained in the form of an oxide, and the compositional ratio of each component was 61.4% by weight of manganese, 19.0% by weight of aluminum and 19.7% by weight of lanthanum in terms of oxides.

A volume of 100 ml reactor manufactured by Inconel 600 was filled with 2 g of a granular catalyst having a size of 1.0 to 1.2 mm and a predetermined amount of hydrogen peroxide (8 mL) was pulsed. Simultaneously with the introduction of high concentration hydrogen peroxide, the temperature of the liquid phase inside the reactor was measured 100 times per second. As a result, 2.1 seconds elapsed after the start of the reaction, and the maximum temperature reached 152.5 ^° C.

After the above-mentioned high-concentration hydrogen peroxide decomposition experiment was completed and the temperature and pressure inside the reactor were recovered to the initial state, the above-mentioned high-concentration hydrogen peroxide decomposition experiment was repeatedly performed while keeping the catalyst in the reactor. After the high concentration hydrogen peroxide decomposition experiment was repeated 15 times, the temperature of the liquid phase in the reactor was measured. As a result, 4.3 seconds passed after the start of the reaction, the maximum temperature reached 127.6 ^° C. After the high-concentration hydrogen peroxide decomposition experiment was repeated 35 times, the temperature of the liquid phase in the reactor was measured. As a result, 4.1 seconds elapsed after the start of the reaction, the maximum temperature reached 164.1 ^° C.

Example 3. Preparation of Metal Catalyst Composition in Metal Foam Form

A precursor aqueous solution was prepared by mixing K-Mn precursor, Mn precursor, Pb, Ni, Cu, Ce, Bi, Pt and Ag precursors in distilled water and stirring the components so that they could be mixed evenly.

Thereafter, the metal foam was immersed in the precursor aqueous solution, and the surface of the metal foam was coated with the precursor aqueous solution. The metal foam includes a plurality of cells, and the cells have a size of 800 mu m to 3000 mu m or less.

The metal foam coated with the precursor aqueous solution was dried at a temperature of 110 DEG C for 12 hours.

The process of immersing the metal foam in the precursor aqueous solution and drying the metal foam was performed a plurality of times.

Thereafter, the metal foams were fired at a temperature of 600 DEG C for 4 hours.

In a 100 ml volume reactor made of Inconel 600, 8 g of a catalyst in the form of a metal foil having a mesh interval of 800 to 3,000 m (8 g of catalyst active material supported) was charged and a predetermined amount of hydrogen peroxide (8 ml) was injected with a pulse. Simultaneously with the introduction of high concentration of hydrogen peroxide, the temperature of the liquid phase in the reactor was measured 100 times per second. As a result, 1.9 seconds elapsed after the start of the reaction, and the maximum temperature reached 165.0 ^° C.

After the above-mentioned high-concentration hydrogen peroxide decomposition experiment was completed and the temperature and pressure inside the reactor were recovered to the initial state, the above-mentioned high-concentration hydrogen peroxide decomposition experiment was repeatedly performed while keeping the catalyst in the reactor. After the high concentration hydrogen peroxide decomposition experiment was repeated 15 times, the temperature of the liquid phase inside the reactor was measured. As a result, 2.6 seconds elapsed after the start of the reaction, the maximum temperature reached 168.1 ^° C. After the high-concentration hydrogen peroxide decomposition experiment was repeated 35 times, the temperature of the liquid phase in the reactor was measured. As a result, 3.9 seconds elapsed after the start of the reaction, and the maximum temperature reached 169.4 ^° C.

Comparative Example

A granular catalyst was prepared in the same manner as in Example 1 except that 52.8 g of manganese nitrate (hexahydrate) and 72.0 g of aluminum nitrate (9 hydrate) were dissolved in 300 ml of distilled water to prepare a metal precursor solution. The composition of the resulting catalyst was obtained in the form of an oxide, and the compositional ratio of each component was 76.4% by weight of manganese and 23.6% by weight of aluminum in terms of oxides.

A volume of 100 ml reactor manufactured by Inconel 600 was filled with 2 g of a granular catalyst having a size of 1.0 to 1.2 mm and a predetermined amount of hydrogen peroxide (8 mL) was pulsed. Simultaneously with the introduction of high concentration of hydrogen peroxide, the temperature of the liquid phase in the reactor was measured 100 times per second. As a result, 2.2 seconds elapsed after the start of the reaction, the maximum temperature reached 147.5 ^° C. After the above-mentioned high-concentration hydrogen peroxide decomposition experiment was completed and the temperature and pressure inside the reactor were recovered to the initial state, the above-mentioned high-concentration hydrogen peroxide decomposition experiment was repeatedly performed while keeping the catalyst in the reactor. After the high-concentration hydrogen peroxide decomposition experiment was repeated 15 times, the temperature of the liquid phase in the reactor was measured. As a result, 340 seconds elapsed after the start of the reaction and the maximum temperature reached 63.1 ^° C, The activity and lifespan of the cells rapidly decreased.

The maximum liquid temperature (T _max ) and the time (t _max ) for reaching the maximum liquid temperature in the high concentration hydrogen peroxide decomposition reaction according to Examples 1 to 3 and Comparative Example of the present invention are shown in Tables 3, 4, 2 and 3 Respectively.

division Catalyst composition
(weight%) Catalyst type
And size Maximum temperature ( ^o C) at decomposition by number of repeated injections of hydrogen peroxide 1 time 15 times 35 times Example 1 Mn: La: Al
(55.8: 17.9: 26.3) Granule type
(Diameter ~ 1 mm) 153.1 164.0 165.6 Example 2 Mn: La: Al
(61.4: 19.7: 19.0) Granule type
(Diameter ~ 1 mm) 152.5 127.6 164.1 Example 3 Mn: K: Pb
(60.0: 20.0: 20.0) Metal foam type (interval: 800 ~ 3,000μm) 165.0 168.1 169.4 Comparative Example Mn: Al
(76.4: 23.6) Granule type
(Diameter ~ 1 mm) 147.5 63.1 Not responded

division Catalyst composition
(weight%) Catalyst type
And size Time required to reach the maximum temperature in the decomposition by the number of repeated injections of hydrogen peroxide (seconds) 1 time 15 times 35 times Example 1 Mn: La: Al
(55.8: 17.9: 26.3) Granule type
(Diameter ~ 1 mm) 2.3 2.6 4.3 Example 2 Mn: La: Al
(61.4: 19.7: 19.0) Granule type
(Diameter ~ 1 mm) 2.1 4.3 4.1 Example 3 Mn: K: Pb
(60.0: 20.0: 20.0) Metal foam type (interval: 800 ~ 3,000μm) 1.9 2.6 3.9 Comparative Example Mn: Al
(76.4: 23.6) Granule type
(Diameter ~ 1 mm) 2.2 340 Not responded

It will be apparent to those skilled in the art that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof.

In addition, the above detailed description should not be construed in all aspects as limiting and should be considered illustrative. The scope of the present invention should be determined by rational interpretation of the appended claims, and all changes within the scope of equivalents of the present invention are included in the scope of the present invention.

Claims (8)

Preparing a mixture by dissolving a manganese compound, an aluminum compound, and a lanthanum precursor in a predetermined solvent;
Precipitating a catalyst in powder form from the mixture and drying the catalyst in the form of a precipitated powder;
Calcining the powdery catalyst at a temperature of 400 to 800 캜;
Mixing a binder solution and methylcellulose in the powdery catalyst, and molding the mixture into a predetermined shape to produce a molded body; And
And firing the molded body at a temperature of 400 to 800 ° C. The method according to claim 1,
In the step of producing the molded body,
Wherein the binder solution is a mixture of a pseudoboehmite solution and an aqueous nitric acid solution,
Wherein the weight ratio of the shudo bohemite to the mass of the catalyst in powder form is 0.05 to 0.2. 3. The method of claim 2,
In the step of producing the molded body,
Wherein the mass ratio of the methyl cellulose to the mass of the catalyst in powder form is 0.01 to 0.1. In the metal catalyst composition,
The composition may comprise,
Manganese oxide, lanthanum oxide, and aluminum oxide,
Wherein the mass ratio of manganese (Mn / Al) to the mass of aluminum contained in the composition is 0.5 to 4.5,
Wherein the mass ratio (La / (Mn + La + Al)) of lanthanum to the total mass of manganese, lanthanum and aluminum contained in the composition is 0.05 to 0.30. Preparing a precursor aqueous solution by mixing at least one of a K-Mn precursor, a Mn precursor, Pb, Ni, Cu, Ce Bi, Pt, and Ag precursors in a predetermined solvent;
Coating the precursor aqueous solution on a surface of a metal foam of a predetermined type;
Drying the metal foam coated with the precursor aqueous solution at a temperature of 100 to 120 DEG C for 10 to 14 hours; And
And calcining the metal foam. The method for producing a metal catalyst composition for decomposing hydrogen peroxide according to claim 1, 6. The method of claim 5,
Wherein the step of preparing the precursor aqueous solution comprises:
At least one of Al ₂ O ₃ and Fe ₂ O ₃ is further mixed,
Wherein the precursor dissolved in the precursor aqueous solution is one of acetate, sulfate, nitrate, and chloride. The method according to claim 6,
Wherein the metal foam is an Ni-Fe-Cr or Ni-Cr-Al alloy. 8. The method according to claim 7,
And calcining the metal foam at a temperature of 600 to 900 ° C for 3 to 5 hours in a state where at least one of nitrogen, air and oxygen is in contact with the metal foam.

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