Activated Carbon Catalyst for Hydrogen Peroxide Decomposition, Method for Producing Same, and Method for Decomposing Hydrogen Peroxide by Using Same

Abstract

Disclosed herein are an activated carbon catalyst for hydrogen peroxide decomposition, a preparation method thereof and a hydrogen peroxide decomposition method using the same. The activated carbon catalyst for hydrogen peroxide decomposition, provided in an aspect of the present invention may be easily prepared through the carbonization and activation of an ion exchange resin, and safer and higher decomposition efficiency of hydrogen peroxide may be achieved than the conventional catalyst for hydrogen peroxide decomposition through the control of the manganese content and pore properties in the catalyst.

Claims

1.-12. (canceled)

13. An activated carbon catalyst for hydrogen peroxide decomposition comprising manganese, wherein the activated carbon catalyst for hydrogen peroxide decomposition is formed from an ion exchange resin.

14. The activated carbon catalyst of claim 13, wherein the manganese is present in an amount of 12 to 16 wt % of the activated carbon catalyst.

15. The activated carbon catalyst of claim 13 further comprising a specific surface area in a range of 1000 to 1200 m.sup.2/g.

16. The activated carbon catalyst of claim 13, wherein the activated carbonized catalyst is prepared by carbonization and activation of an ion exchange resin modified to contain manganese through ion exchange.

17. The activated carbon catalyst of claim 13, wherein the activated carbonized catalyst comprises a spherical shape.

18. The activated carbon catalyst of claim 17, wherein the activated carbonized catalyst has an average diameter in a range of 0.1 to 5.0 mm.

19. A method for preparing an activated carbon catalyst comprising the steps of: a) immersing an ion exchange resin in a manganate (II) solution; b) performing ion exchange thereby transporting manganese from the manganate (II) solution to the immersed ion exchange resin, thereby forming an ion exchanged ion exchange resin; c) drying the ion exchanged ion exchange resin; and d) heating the dried ion exchange resin to carbonize and activate the dried ion exchange resin, thereby forming the activated carbon catalyst.

20. The method of claim 19, wherein the manganate (II) is selected from the group consisting of manganese nitrate, manganese acetate, manganese chloride, manganese acetylacetonate, manganese bromide, manganese carbonate, manganese fluoride, manganese iodide, manganese sulfate, and combinations thereof.

21. The method of claim 19, wherein the drying step is performed at 50 to 150° C.

22. The method of claim 19, wherein the heating step is performed at 800 to 1100° C.

23. An apparatus for hydrogen peroxide decomposition comprising the activated carbon catalyst of claim 13.

24. A method for the decomposition of hydrogen peroxide, the method comprising the steps of: immersing the activated carbon catalyst of claim 13 in hydrogen peroxide thereby decomposing the hydrogen peroxide into water and oxygen; and recovering a remaining activated carbon catalyst.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:

[0019] FIG. 1 is a diagram showing a reaction apparatus used in a step of carbonization and activation during preparing an activated carbon catalyst for hydrogen peroxide decomposition, provided in an aspect of the present invention.

[0020] FIG. 2 is a diagram showing comparison results on the decomposition efficiency of hydrogen peroxide in accordance with diverse manganese contents in a catalyst.

[0021] FIG. 3 is a diagram showing comparison results on the decomposition efficiency of hydrogen peroxide in accordance with diverse specific surface areas in a catalyst.

[0022] FIG. 4 is a diagram showing spherical activated carbon (70×) which do not carry a metal.

[0023] FIG. 5 is a diagram showing Example 1-1 (70×).

[0024] FIG. 6 is a diagram showing Example 1-4 (70×).

[0025] FIG. 7 is a diagram showing Example 1-5 (70×).

[0026] FIG. 8 is a diagram showing Example 1-9 (70×).

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] Hereinafter, the present invention will be explained in detail.

[0028] Meanwhile, the embodiments of the present invention could be modified into various other types, and the scope of the present invention is not limited to embodiments explained below. In addition, the embodiments of the present invention are provided for explaining the present invention more completely to a person having average knowledge in this technical field. Further, “comprising” a certain constituent element throughout the specification means the further inclusion of other constituent elements but does not preclude the other constituent elements unless otherwise described to the contrary.

[0029] An aspect of the present invention provides an activated carbon catalyst containing manganese for hydrogen peroxide decomposition, wherein the activated carbon catalyst for hydrogen peroxide decomposition is characterized in being formed from an ion exchange resin.

[0030] In this case, the manganese may be included in a range of 12 to 16 wt %, may be included in a range of 13 to 16 wt %, may be included in a range of 14 to 16 wt %, may be included in a range of 12 to 15 wt %, may be included in a range of 12 to 14 wt %, may be included in a range of 13 to 15 wt %, or may be included in a range of 14 wt %, in 100 wt % of the activated carbon catalyst for hydrogen peroxide decomposition, but the manganese content is not limited to a specific value.

[0031] In addition, the specific surface area of the activated carbon catalyst for hydrogen peroxide decomposition may be in a range of 1000 to 1200 m.sup.2/g, in a range of 1020 to 1200 m.sup.2/g, in a range of 1040 to 1200 m.sup.2/g, in a range of 1060 to 1200 m.sup.2/g, in a range of 1080 to 1200 m.sup.2/g, in a range of 1100 to 1200 m.sup.2/g, in a range of 1000 to 1180 m.sup.2/g, in a range of 1000 to 1160 m.sup.2/g, in a range of 1000 to 1140 m.sup.2/g, in a range of 1000 to 1120 m.sup.2/g, in a range of 1000 to 1100 m.sup.2/g, in a range of 1020 to 1180 m.sup.2/g, in a range of 1040 to 1160 m.sup.2/g, in a range of 1060 to 1140 m.sup.2/g, in a range of 1080 to 1120 m.sup.2/g, in a range of 1100 m.sup.2/g, but the specific surface area is not limited to a specific value.

[0032] The activated carbon catalyst for hydrogen peroxide decomposition may be prepared by the carbonization and activation of an ion exchange resin which is ion exchanged and includes manganese. In addition, the activated carbon catalyst for hydrogen peroxide decomposition may have a spherical shape, and the activated carbon catalyst for hydrogen peroxide decomposition with a spherical shape may have an average diameter in a range of 0.1 to 5.0 mm, in a range of 0.2 to 5.0 mm, in a range of 0.3 to 5.0 mm, in a range of 0.1 to 4.0 mm, in a range of 0.1 to 3.0 mm, in a range of 0.1 to 2.0 mm, in a range of 0.1 to 1.0 mm, in a range of 0.1 to 5.0 mm, in a range of 0.1 to 1.0 mm, in a range of 0.1 to 0.5 mm, in a range of 0.1 to 0.3 mm, in a range of 0.2 to 1.0 mm, and in a range of 0.3 to 0.5 mm, but the average diameter is not limited to a specific value.

[0033] In another aspect of the present invention, there is provided a preparation method of an activated carbon catalyst for hydrogen peroxide decomposition, including:

[0034] immersing an ion exchange resin in a manganate (II) solution to perform ion exchange so that manganese is contained in the ion exchange resin;

[0035] drying the ion exchanged ion exchange resin; and

[0036] heating the dried ion exchange resin for carbonization and activation.

[0037] In this case, the manganate (II) may use manganese nitrate, manganese acetate, manganese chloride, manganese acetylacetonate, manganese bromide, manganese carbonate, manganese fluoride, manganese iodide, manganese sulfate, etc. solely, or combinations thereof, without specific limitation.

[0038] The drying may be performed at 50 to 150° C., and the heating may be performed at 800 to 1100° C., without specific limitation.

[0039] Another aspect of the present invention provides a decomposition apparatus of hydrogen peroxide, including the activated carbon catalyst for hydrogen peroxide decomposition.

[0040] Further another aspect of the present invention provides a decomposition method of hydrogen peroxide, including:

[0041] immersing the activated carbon catalyst for hydrogen peroxide decomposition in hydrogen peroxide to decompose the hydrogen peroxide into water and oxygen; and

[0042] recovering a remaining catalyst.

[0043] The activated carbon catalyst for hydrogen peroxide decomposition, provided in an aspect of the present invention may be easily prepared through the carbonization and activation of an ion exchange resin, and through the control of the manganese content and pore properties in the catalyst, effects of accomplishing safer and higher decomposition efficiency of hydrogen peroxide than the conventional catalyst for hydrogen peroxide decomposition may be obtained, and these may be directly supported by Examples and Experimental Examples, described below.

<Example 1> Preparation of Activated Carbon Catalyst for Hydrogen Peroxide Decomposition

[0044] The activated carbon catalyst for hydrogen peroxide decomposition, provided in an aspect of the present invention was prepared as follows.

[0045] Into an aqueous solution including Mn(NO.sub.3).sub.2, an ion exchange resin (gel type strongly acidic cation resin with a product name of AMBERLITE™ IRC 120 H Ion Exchange Resin, purchased from Dow Chemical Co.) was immersed to induce ion exchange. Hence, an ion exchange resin carrying manganese was obtained, and this was dried at 100° C. for one day. Then, heating at 900° C. was performed under a nitrogen (N.sub.2) atmosphere for the carbonization and activation of the ion exchange resin to prepare an activated carbon catalyst for hydrogen peroxide decomposition. A reaction apparatus used for preparing the activated carbon catalyst for hydrogen peroxide decomposition is shown in FIG. 1.

[0046] The manganese content (wt %) and specific surface area (m.sup.2/g) in the catalyst were controlled by controlling the concentration of an aqueous solution including Mn(NO.sub.3).sub.2 (i.e., a precursor solution), and time for carbonization and activation, and the results are shown in Table 1 and Table 2 below.

TABLE-US-00001 TABLE 1 Concentration of precursor Mn BET specific solution used during content surface area PV.sub.meso PV.sub.micro preparing catalyst and Example (wt %) (m.sup.2/g) (cm.sup.3/g)* (cm.sup.3/g)* activation time 1-1  5% 1124 0.36 0.34 0.1 N, 5 h   (51%) (49%) 1-2 10% 1122 0.32 0.34 0.2 N, 5 h   (48%) (52%) 1-3 14% 1116 0.81 0.27 0.3 N, 5.5 h (75%) (25%) 1-4 18% 1118 0.87 0.27 0.3 N, 6.5 h (76%) (24%)

TABLE-US-00002 TABLE 2 Concentration of precursor Mn BET specific solution used during content surface area PV.sub.meso PV.sub.micro preparing catalyst and Example (wt %) (m.sup.2/g) (cm.sup.3/g)* (cm.sup.3/g)* activation time 1-5 14% 500 0.12 0.16   1 N, 1.5 h (43%) (57%) 1-6 14% 780 0.39 0.23 0.5 N, 3.5 h (63%) (37%) 1-7 14% 1100 0.81 0.27 0.3 N, 5.5 h (75%) (25%) 1-8 14% 1330 0.83 0.21 0.2 N, 8 h   (80%) (20%) 1-9 14% 1450 0.95 0.16 0.18 N, 7 h   (86%) (14%) *The values in parentheses are percent values with respect to total pore volume (PV.sub.meso + PV.sub.micro)

<Experimental Example 1> Evaluation on Decomposition Efficiency of Hydrogen Peroxide According to Manganese Content

[0047] The decomposition efficiency of hydrogen peroxide according to the manganese content in the activated carbon catalyst for hydrogen peroxide decomposition, provided in an aspect of the present invention, was evaluated as follows.

[0048] 0.05 g of each of the activated carbon catalysts prepared in Examples 1-1 to 1-4 and 200 cc of a 30% (v/v) hydrogen peroxide solution were reacted. The reaction was conducted in a glass reactor with a volume of 500 ml. 200 cc of the 30% (v/v) hydrogen peroxide solution was charged in the reactor, and 0.05 g of the activated carbon catalyst prepared was put in a catalyst container. In a closed state of the reactor, the container was dropped into the hydrogen peroxide solution to initiate the reaction. An oxygen gas produced through the reaction was passed through a vapor trap to remove vapor, and then, passed through a mass flow meter, and a flow rate was measured every 30 seconds.

[0049] The results are shown in FIG. 2.

[0050] As shown in FIG. 2, the catalyst of Example 1-3, including 14 wt % of manganese in total 100 wt % of the catalyst showed most excellent decomposition efficiency of hydrogen peroxide. From this, the catalyst including 14 wt % of manganese may induce an oxygen generation profile most consistently.

<Experimental Example 2> Evaluation on Decomposition Efficiency of Hydrogen Peroxide According to Pore Properties

[0051] In order to evaluate the decomposition efficiency of hydrogen peroxide according to pore properties in the activated carbon catalyst for hydrogen peroxide decomposition, provided in an aspect of the present invention, the decomposition efficiency of hydrogen peroxide was evaluated by the same method as in Experimental Example 1 using the activated carbon catalysts prepared in Examples 1-5 to 1-9.

[0052] The results are shown in FIG. 3.

[0053] As shown in FIG. 3, the activated carbon catalysts having a specific surface area of 1000 m.sup.2/g or less, showed a rapid reaction rate at an initiation stage, and then showed a rapidly reduced production flow rate of oxygen of 0.5 L/min. For reasons, for favorable reaction in an aqueous phase, the development of pores with a meso size is important, but in case of the catalysts, a total pore volume was small, and in addition, the percent of a meso pore volume was less than 70% and insufficient, a reaction solution (hydrogen peroxide) could not easily diffuse into the pores but made a contact with only the active site at the surface of the activated carbon, and thus, it is judged that the reaction activity was shown at an initiation stage. However, in case of activated carbon catalysts having a specific surface area of 1000 m.sup.2/g-1400 m.sup.2/g, a production flow rate of oxygen tended to be kept relatively constant. These had the percent of meso pore volume of 70%-80%, and meso pores were sufficiently formed so that a reaction solution could easily diffuse into the pores, and a gas (oxygen) could be easily exhausted for smooth exchange of the reactants and products. On the contrary, in case of a catalyst having a specific surface area of 1450 m.sup.2/g, the results of lower activity than a catalyst with 1330 m.sup.2/g were shown. It could be found that these results were shown by the collapse of the pores through the over activation of the specimen with 1450 m.sup.2/g. Accordingly, it could be found that the performance of an activated carbon catalyst is closely related to pore properties including a pore volume formed, forming ratio of meso and micro pores, etc.

INDUSTRIAL APPLICABILITY

[0054] The activated carbon catalyst for hydrogen peroxide decomposition, provided in an aspect of the present invention may be easily prepared through the carbonization and activation of an ion exchange resin, and safer and higher decomposition efficiency of hydrogen peroxide than the conventional catalyst for hydrogen peroxide decomposition may be achieved through the control of the manganese content and pore properties in the catalyst.